Preparation and uses of bio-adhesives

ABSTRACT

The present application relates generally to bio-adhesive components isolated from bio-oil prepared from animal waste, methods of preparation of the bio-adhesive components and uses thereof. Such uses include, but are not limited to, asphalt bio-binders, bio-adhesion promoters, asphalt bio-rejuvenators, asphalt bio-extenders, bio-asphalt as well as uses in roofing, soil stabilization, crack and joint sealing and flooring adhesives.

RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.14/032,445, filed on Sep. 20, 2013, now U.S. Pat. No. 9,637,615, thedisclosure of which is incorporated herein by reference in its entirety,and which claims priority under 35 U.S.C. § 119(e) to U.S. ProvisionalPatent Application Ser. Nos. 61/782,547, filed Mar. 14, 2013, and61/704,175, filed Sep. 21, 2012, the disclosure of each of which isincorporated herein by reference in its entirety.

STATEMENT AS TO RIGHTS TO INVENTIONS MADE UNDER FEDERALLY SPONSOREDRESEARCH OR DEVELOPMENT

This invention was made with government support under Grant Nos.IIP-1246330, CMMI-1150695, CBET-1040246, CBET-0923425, and 0955001awarded by the National Science Foundation. The government has certainrights in the invention.

FIELD

The present inventions relate generally to bio-adhesive componentsisolated from bio-oil prepared from animal waste, methods of preparationof the bio-adhesive components and uses thereof.

BACKGROUND

According to the USDA, “the combined value of production from broilers,eggs, turkeys, and the value of sales from chickens in 2011 was $35.6billion . . . . Of the combined total, 65 percent was from broilers, 21percent from eggs, 14 percent from turkeys, and less than 1 percent fromchickens.” (USDA, National Agricultural Statistics Service“Poultry—Production and Value 2011 Summary” (April 2012)) According tothe US EPA the composition of solid manure from pullets and laying hensin layer cages can range in dry matter between 20% and 60% andsemi-solid manure contains 12 to 20% solids. (US EPA| Ag 101| PoultryProduction, www.epa.gov/oecaagct/ag101/printpoultry.html). Poultrymanure is typically used in surface applications to croplands.

Within the United States, pork production is a major agriculturalenterprise; specifically, a gross income of roughly $16 billion resultedfrom the sale of 116 million pigs in 2008. In general, pigs weighing 21to 100 kg generate 0.39 to 0.45 kg of waste per day per pig on a drymatter basis. Swine manure is usually disposed of by storage in lagoons.This process has significant negative environmental impacts,particularly with respect to surface water and groundwater quality aswell as air quality, which is affected by odors and gaseous emissions.

Dairy and beef production are similarly important components of U.S.agricultural efforts. Removal or treatment of animal waste isanalogously a key consideration as the number of cows raised in the U.S.trends upwards.

To improve the ultimate processing of beef, dairy, poultry, sheep andswine manure, researchers have developed methods to convert manure togas and/or oil. Collection of manure is easier in confined animalfeeding operations, due in part to bulk processing of waste, as well asthe controlled diet of the animals. Bio-oil produced from animal wasteis an energy-dense crude oil that is similar to petroleum extracts.By-products of bio-oil produced from animal waste include an aqueousphase and a solid phase; uses for both by-products have been identifiedin the art.

Petroleum-based products, such as adhesives, are used in pavementconstruction as asphalt binders, adhesion promoters, asphalt extendersand asphalt concrete. In addition they are used in roofing, soilstabilization, crack and joint sealing and as flooring adhesives.

The U.S. asphalt market is valued at approximately $11.7 billion/year.Asphalt supplies are shrinking, while the demand for it is increasingrapidly. As the price of asphalt increases, the demand for alternativeand renewable resources increases.

The trend toward sustainable pavements has led the pavement industry toemphasize use of recycled materials, including rubber from tires and flyash as well as reclaimed asphalt pavement (RAP) and recycled asphaltshingles (RAS) in pavement construction. Use of these recycled productsreduces the environmental liability of RAP and RAS and further reducesthe amount of virgin asphalt used in pavement construction. In the U.S.,about 100 million tons of RAP and 11 million tons of RAS are producedannually. Because asphalt in both RAP and RAS is much stiffer thanvirgin asphalt, inclusion of RAP and/or RAS lead to a significantincrease in the stiffness of the resulting recycled-asphalt mixture.Stiff asphalt mixtures have been shown to be hard to place andsusceptible to cracking a lower temperatures. Addressing these factorsis an important challenge to the use of high percentages of RAP and RASin pavement construction.

Hot-mix asphalt production is the most common paving approach in theUnited States; however, concerns about the process's environmentalpollution continue to grow because of the emission of greenhouse gasesduring the construction of hot-mix pavement. To address these concerns,a new group of technologies has been developed for asphalt pavementproduction. These technologies, called warm mix asphalt (WMA), allowproducers of asphalt pavement material to lower the temperatures atwhich the material is mixed and placed on the road. Reductions of 50° F.to 100° F. have been observed. Reducing production temperature resultsin reduced fuel consumption as well as reduced greenhouse emissions, andimproves job site conditions for workers. Lower production temperaturealso reduces the initial aging of the binder, which can improvelong-term durability and pavement performance. To produce WMA, severaldifferent technologies and additives have been used along with asphaltbinder to reduce viscosity of the binder. However, most of theseadditives are petroleum-based and costly.

Despite the large market for scrap tires, roughly a quarter of all scraptires end up in landfills each year numbering to approximately 27million tires or roughly 6 million tons annually making up over 12% ofall solid waste. Due to cross-linking between the rubber polymer chains,numerous additives, and stabilizers within its structure, rubber isextremely resistant to natural degradation making it troublesome forlandfill storage. Crumb rubber's use in asphalt binder and pavementsprovides an environmentally sustainable method for disposing themillions of tires generated annually. Generally, tires are ground usingambient or cryogenic means, the goal of which is to reduce the size ofthe rubber into a fine powder of particle sizes smaller than 2 mm indiameter. The rubber can be used in a variety of uses, including amodifier for petroleum-based asphalt binder. The modification of asphaltmixture with rubber is typically classified into three differentmethods: (a) Dry Process, which uses crumb rubber as an aggregatesubstitute; (b) Wet Process with Agitation, in which large particles(particles not passing No. 50 Sieve) are blended with the binder whileapplying agitation during mixing to keep crumb rubber particlesuniformly distributed; and (c) Wet Process with no Agitation, in whichsmall particles (passing No. 50 Sieve) are blended with asphalt binderwith no agitation.

One important variable in asphalt concrete pavements is adhesion betweenaggregate and asphalt/bitumen. Adhesion promoters, also known asanti-strips, are used to improve the interaction between asphalt and theaggregates comprising asphalt concrete. Changes to the use of asphaltconcrete pavements and advances in technology have led to an increasedneed for adhesion promoters of particular characteristics. Inparticular, users are looking for asphalt pavements having longerlifespans, but over which the pavements will be subjected to increasingtraffic loads. Adhesion promoters are used for a variety of goals,including by not limited to mitigating and inhibiting the damagingeffects of moisture in asphalt pavements. Water damage is manifest in anumber of ways, which can lead to potholes, for example, freeze-thawcycles exacerbate the effect of water damage. On the molecular level theresult of water damage is the loss of adhesion between the binder andthe aggregate, also known as stripping. The majority of current adhesionpromoters are petroleum-based and suffer from increasing demand andcorrespondingly cost, while supplies are shrinking. A source ofnon-petroleum based adhesion promoters is needed in the industry.

Asphalt rejuvenators are generally used to restore the balance betweenmaltenes and asphaltenes in asphalt binder that has been disturbed overtime due to progressive aging. Because of weathering or oxidation, theratio of maltenes to asphaltenes is changed as some of the maltenescompounds are transformed to asphaltenes component over time. Theeffectiveness of a rejuvenator is typically evaluated by whether it canrestore the maltene/asphaltene balance; targeted rejuvenators usuallycontain maltenes-type fractions to improve and balance the maltenes toasphaltenes ratio. To evaluate its effectiveness as a rejuvenator a testmethod, including but not limited to asphalt penetration, viscosity, orabrasion loss test are used.

Asphalt rejuvenators are usually formulated to revive an aging pavement,improving the composition of the asphalt cement and increase penetrationvalue of the asphalt cement in the top portion of the pavement therebyincreasing the durability and lifespan of the pavement and to sealpavement against air and water, thereby slowing oxidative degradation.Typically, rejuvenators are used on asphalt pavement to stop and/orreverse shrinking which can lead to hairline cracking, to inhibitpitting and raveling, and to reduce air and water permeability, whichcan lead to pavement degradation. Asphalt rejuvenators can be used inasphalt rehabilitation as well as hot-in place and cold-in placerecycling.

Asphalt extenders are generally petroleum-based products enabling therecycling of asphalt waste, such as RAP, RAS, as well as natural asphaltsources such as rock asphalt, tar sands, Gilsonite, and Trinidad LakeAsphalt. Asphalt extenders enable a larger amount of asphalt wastematerial to be used in a performance grade asphalt mix, thereby reducingthe cost of the performance grade asphalt mix having the targetedmechanical and physical properties. Alternate sources of asphaltextenders are needed in the industry, particular as petroleum sourcesbecome ever more expensive and continue to raise environmental concerns.

The above-identified needs in the asphalt industry have motivatedseveral unsuccessful attempts by researchers to produce bio-asphalt fromvarious materials (sugar, molasses, potato starches, vegetable oils,lignin, cellulose, palm oil waste, coconut waste, and dried sewage).However, those bio-asphalts either found not to be feasible or neverreached the asphalt market due to low performance or high productioncost.

Thus, there remains a need for non-petroleum based asphalt that can beused in pavement construction. In particular, there is a need forasphalt bio-binders, bio-adhesion promoters, asphalt bio-rejuvenators,asphalt bio-extenders as well as bio-asphalt. In addition, there is aneed for bio-adhesives that can be used roofing, soil stabilization,crack and joint sealing and as flooring adhesives.

SUMMARY

The present application is generally directed to the production ofbio-adhesives having targeted viscosities. As disclosed herein,bio-adhesive components can be prepared from a bio-oil isolated fromanimal waste, including but not limited to beef, dairy, swine, poultry,sheep manures or combinations thereof.

In one aspect, the present application discloses a method of isolating abio-adhesive composition from a bio-oil, the method comprising: (a)providing a bio-oil derived from animal waste; (b) distilling thebio-oil to remove a light liquid fraction, wherein the distilling occursat a vacuum pressure of between about 1 mm Hg and about 80 mm Hg whileheating to a temperature of up to about 60° C., optionally wherein therate of the heating is between about 5° C. per hour and about 50° C. perhour; and (c) isolating a bio-adhesive composition from the bio-oilunder conditions such that the viscosity of the bio-adhesive compositionis not allowed to exceed about 1 centipoise (cP) at 135° C., optionallywherein the viscosity of the bio-adhesive composition is not allowed toexceed about 0.5 cP at 135° C.

In another aspect, the present application discloses a method ofisolating a bio-adhesive composition from a bio-oil, the methodcomprising: (a) providing a bio-oil derived from animal waste; (b)distilling the bio-oil to provide a distilled heavy liquid fraction anda bio-residue that is not distilled, wherein the distilling occurs undervacuum pressure, optionally of between about 1 mm Hg and about 80 mm Hg,while heating to (1) a temperature ranging from about 60° C. to about100° C., or (2) a temperature ranging from about 100° C. to about 160°C., wherein the viscosity of the bio-residue is not allowed to exceedabout 1 cP at 135° C., optionally wherein the viscosity of thebio-residue is not allowed to exceed about 0.5 cP at 135° C. and furtheroptionally wherein the rate of the heating is between about 5° C. perhour and about 50° C. per hour; and (c) isolating the bio-adhesivecomposition comprising the heavy liquid fraction.

In yet another aspect the present application discloses a bio-adhesivecomposition produced by any method disclosed herein.

In one aspect, the present application discloses a bio-adhesivecomposition comprising a heavy liquid fraction and a bio-residue,wherein the composition has a viscosity of at least about 0.5 cP at 135°C., optionally between about 0.5 cP and about 1 cP at 135° C. whereinsaid heavy liquid fraction and bio-residue are isolated from bio-oilproduced from animal waste and wherein said bio-adhesive compositiondoes not contain a light liquid fraction.

In another aspect, the present application discloses a bio-adhesivecomposition comprising a heavy liquid fraction having a viscosity ofbetween about 0.1 cP and 0.5 cP at 135° C., optionally, between about0.2 cP and about 0.5 cP, wherein said bio-adhesive composition does notcontain a light liquid fraction and wherein said heavy liquid fractionis isolated from bio-oil produced from animal waste.

In one variation, the bio-adhesive composition comprises (a) a heavyliquid fraction comprising at least about 5% by weight ofamide-containing compounds, optionally containing about 10% to about 20%by weight of amide-containing compounds, or (b) a heavy liquid fractioncomprising up to about 5% by weight of amide-containing compounds,optionally about 1% to about 5% by weight of amide-containing compounds,wherein said bio-adhesive composition does not contain a light liquidfraction.

In another variation, the present application discloses a bio-adhesivecomposition comprising a bio-residue having a viscosity of at leastabout 0.4 cP, optionally between about 0.5 cP and 1 cP, at 135° C.,wherein said bio-adhesive composition does not contain a light liquidfraction and wherein said bio-residue is isolated from bio-oil producedfrom animal waste.

In yet another variation, the present application discloses abio-adhesion promoter comprising a bio-adhesive composition disclosedherein, optionally wherein the bio-adhesive composition comprises atleast about 5% by weight amide-containing compounds. In anothervariation, the present application discloses an asphalt bio-extendercomprising a bio-adhesive composition as disclosed herein optionally incombination with an asphalt binder. In one variation, the presentapplication discloses a bio-rejuvenator for asphalt compositions, thebio-rejuvenator comprising a bio-adhesive composition as disclosedherein, optionally in combination with an asphalt binder. The presentapplication also discloses a bio-modified binder comprising abio-adhesive composition disclosed herein.

Also disclosed herein is a bio-modified composition comprising abio-adhesive composition disclosed herein optionally in combination withasphalt, further optionally wherein the asphalt is recycled asphalt.Further disclosed herein is a rubber-containing bio-asphalt compositioncomprising a bio-adhesive composition as disclosed herein, incombination with rubber and optionally comprising an asphalt binderand/or an aggregate other than rubber. Also disclosed herein is ananoclay-containing bio-asphalt comprising a bio-adhesive composition asdisclosed herein in combination with nanoclay and optionally comprisingan asphalt binder and/or an aggregate other than nanoclay.

In one aspect, the present application discloses a method of makingbio-modified asphalt composition comprising contacting components for anasphalt composition with a bio-adhesion promoter disclosed herein. Inanother aspect, the present application discloses a method of making abio-modified asphalt composition comprising contacting components for anasphalt composition with an asphalt bio-extender as disclosed herein.The present application also discloses a method of rejuvenating asphaltpavement, comprising contacting an asphalt composition with abio-rejuvenator disclosed herein. In another aspect, the presentapplication discloses a method of covering a surface with a bio-modifiedasphalt composition, comprising contacting the surface with acomposition disclosed herein, optionally wherein the surface is a roof,a road, a floor, a crack or a joint. In yet another aspect, the presentapplication discloses a method of sealing a crack or joint in asphaltpavement comprising applying a bio-modified composition disclosedherein.

In one aspect, the present application discloses a method of isolating abio-adhesive composition from a bio-oil, the method comprising: (a)providing a bio-oil derived from animal waste; (b) distilling thebio-oil to remove a light liquid fraction, wherein the distilling occursat a vacuum pressure of between about 1 mm Hg and about 80 mm Hg whileheating at a rate of between about 5° C. per hour and about 50° C. to atemperature of up to 60° C.; (c) isolating a bio-adhesive compositionfrom the bio-oil under conditions such that the viscosity of thebio-adhesive composition is not allowed to exceed 1 centipoise (cP) at135° C.

In another aspect, the present application discloses a method ofisolating a bio-adhesive composition from a bio-oil, the methodcomprising: (a) providing a bio-oil derived from animal waste; (b)distilling the bio-oil to provide a distilled heavy liquid fraction anda bio-residue that is not distilled, wherein the distilling occurs undervacuum pressure while heating at a rate of between about 5° C. per hourand about 50° C. per hour to (1) a temperature ranging from 60° C. to100° C., or (2) a temperature ranging from 100° C. to 160° C., whereinthe viscosity of the bio-residue is not allowed to exceed 1 cP at 135°C.; and (c) isolating the bio-adhesive composition comprising the heavyliquid fraction.

In yet another aspect, the present application discloses a bio-adhesivecomposition produced by any of the methods disclosed herein. In onevariation, the present application is directed to a bio-adhesivecomposition, comprising a heavy liquid fraction and a bio-residue,wherein the composition has a viscosity of about 0.5 cP at 135° C.wherein said heavy liquid fraction and bio-residue is isolated frombio-oil produced from animal waste and wherein said bio-adhesivecomposition does not contain a light liquid fraction. In anothervariation, the present application is directed to a bio-adhesivecomposition, comprising a heavy liquid fraction having a viscosity ofbetween about 0.1 cP and 0.5 cP at 135° C., optionally, between about0.2 cP and about 0.5 cP, wherein said bio-adhesive composition does notcontain a light liquid fraction. In another variation, the presentapplication is directed to a bio-adhesive composition, comprising abio-residue having a viscosity of at least about 0.4 cP, optionallybetween about 0.5 cP and 1 cP, at 135° C., wherein said bio-adhesivecomposition does not contain a light liquid fraction.

The present application further discloses a bio-adhesion promotercomprising a bio-adhesive composition disclosed herein. In yet anotheraspect, the present application discloses a method of makingbio-modified asphalt composition, comprising contacting components foran asphalt composition with a bio-adhesion promoter as disclosed herein.

The present application additionally discloses an asphalt bio-extendercomprising a bio-adhesive composition disclosed herein and optionally anasphalt binder. In a further aspect, the present application discloses amethod of making a bio-modified asphalt composition, comprisingcontacting components for an asphalt composition with an asphaltbio-extender disclosed herein.

The present application further discloses a bio-rejuvenator comprising abio-adhesive composition disclosed herein and optionally an asphaltbinder. In yet another aspect, the present application discloses amethod of rejuvenating asphalt pavement, comprising contacting anasphalt composition with a bio-rejuvenator as disclosed herein.

In yet another aspect, the present application discloses a bio-modifiedbinder comprising a bio-adhesive composition disclosed herein, andoptionally containing asphalt.

In one aspect the present application discloses a rubber-containingbio-asphalt composition comprising a bio-adhesive composition asdisclosed herein, rubber and optionally an asphalt binder. In anotheraspect, the present application discloses nanoclay-containingbio-asphalt comprising a bio-adhesive composition as disclosed herein,nanoclay and optionally an asphalt binder. In one variation, the presentapplication discloses a method of covering a surface with a bio-modifiedasphalt composition, comprising contacting the surface with acomposition disclosed herein. In another variation, the presentapplication discloses a method of sealing a crack or joint in asphaltpavement comprising applying a bio-modified composition as disclosedherein.

These and other objects and aspects of the present inventions willbecome apparent to those skilled in the art after a reading of thefollowing description of the disclosure when considered with thedrawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A and FIG. 1B provide schematics summarizing processing andcorresponding products/components in accordance with the presentlydisclosed subject matter.

FIG. 2 provides a general schematic outlining of one possible processingequipment arrangement for the input of raw materials and the output ofthe targeted components. Such a process can be continuous or batch andcan be completed by interconnected equipment or separately configuredequipment depending on the available facilities and identified needs.

FIG. 3 is a bar graph comparing adhesion strength between asphalt binderand bio-modified binders comprising 5% by weight bio-binder.

FIG. 4 is a bar graph comparing the m-value, as determined via BendingBeam Rheometer, of petroleum-based asphalt compared to bio-modifiedbinder, comprising 2%, 5% or 10% bio-binder by weight.

FIG. 5A is a graph of reduced frequency vs. dynamic modulus ofRAP-containing asphalt mixtures compared to samples including abio-adhesive of the present application.

FIG. 5B is a bar graph of dynamic modulus for each mixture type at 4° C.at a frequency of 10 Hz.

FIG. 5C is a graph of mixture workability test results of RAP-containingasphalt mixtures compared to samples including a bio-adhesive of thepresent application.

FIG. 6A is a graph of the change in viscosity vs. change in temperaturein rubber-containing asphalts comprising asphalt binder or bio-modifiedbinder.

FIG. 6B is a graph of the change in viscosity vs. change in temperaturein rubber-containing asphalts comprising asphalt binder or bio-modifiedbinder.

FIG. 7A is a bar graph showing the effect on aging index whennanoparticle-containing asphalts are combined with bio-modified binder.

FIG. 7B-1 is a graph showing effect on viscosity whennanoparticle-containing asphalts are combined with bio-modified binder.FIG. 7B-2 is an expanded version of FIG. 7B-1 showing the relationshipbetween temperature in the viscosity range 0.1 to 1.0 Pa·s⁻¹.

It will be understood that the drawings are for the purpose ofdescribing a preferred embodiment of the inventions and are not intendedto limit the inventions thereto.

DETAILED DESCRIPTION

Referring now to FIGS. 1A and 1B, representative process flows inaccordance with the presently disclosed subject matter are schematicallypresented, and generally referred to as 100 and 100′. Animal waste 102(typically composed of 80% water and 20% solids) is subjected tothermochemical conversion 104 to produce solid 108, bio-oil 106 andblack water 110. Solid 108 and bio-oil 106 are subjected to filtrationand fractionation 112. Filtration and fractionation 112 producesbio-char 114 from solid 108 and bio-oil 106. Additionally, filtrationand fractionation 112 produces a light liquid fraction 116, a heavyliquid fraction 118 and a bio-residue 120 from bio-oil 106. Bio-char 114can be provided for bio-soil amendment 124. Light liquid fraction 116,heavy liquid fraction 118, and bio-residue 120 can be subject tooptional post-processing 122 to produce biofuels 126, bio-rejuvenator128, bio-adhesion promoter 130, bio-extender 132, bio-binder 134, andbio-asphalt 136.

Referring particularly to FIG. 1B, bio-oil 106 can be subjected toalternative filtration and fractionation 112′, described herein below,to produce light liquid fraction 116′ and heavy liquid fraction plusbio-residue 120′. Heavy liquid fraction plus bio-residue 120′ can besubjected to optional post-processing 122′ to produce bio-binder 134′and bio-asphalt 136′, in accordance with approaches also set forthherein below.

Referring now to FIG. 2, a system for preparing a bio-adhesivecomposition in accordance with the presently disclosed subject matter isreferred to generally at 200. System 200 includes filtration tank 202wherein a mixture 204 of bio-oil plus solvent plus bio-char material isloaded. After filtration, removing biochar (108 in FIG. 1) filtrate 204′is transferred in the direction of arrow A into vacuum chamber 206 forvacuum distillation. Vacuum gauge 208 is used to monitor pressures invacuum chamber 206. Heater 222 provides heat to vacuum chamber 206.Filtrate 204″forms fractions: a solvent fraction 210, a Light LiquidFraction 212 and Heavy Liquid Fraction/bioresidue 214. In someembodiments, solvent fraction 210, Light Liquid Fraction 212, and HeavyLiquid Fraction 214 flow into condenser 215 for further processing asdisclosed herein below. In some embodiments, Heavy LiquidFraction/bioresidue 214 is pumped into desiccator 216 via discharge pump218, which is controlled by low flow switch 220. A product P flows outof desiccator 216 for isolation.

Continuing with reference to FIG. 2, in some embodiments, condensedLight Liquid Fraction 212 and condensed Heavy Liquid Fraction 214sequentially flow into tank 224, which is in flow communication withcondenser 215 via high level switch 226. Each liquid condensate isdrained from tank 224 via valve 234 for isolation. Alternatively or inaddition, each liquid condensate from tank 224 is pumped into secondvacuum chamber 230 for further processing and interactions as disclosedherein below.

In accordance with the present application and as used herein, thefollowing terms are defined with the following meanings, unlessexplicitly stated otherwise.

“Thermochemical conversion” or “thermochemical liquefaction” refers tothe process converting a liquid slurry of biomass and organic materialsto hydrocarbon oils and byproducts using high pressure (generallybetween about 15 MPa and 20 MPa) and temperature (generally up to 350°C.) in a zero or low oxygen atmosphere. By-products typically includesolids and an aqueous fraction. The quantity and quality of theend-products are typically dependent on the reactor system used andfeedstock characteristics.

As used herein, “bio-oil” refers to an oil produced from animal wastecomprising beef, dairy, swine, poultry, sheep manures, or combinationsthereof. The oil is typically an energy-dense crude oil that is similarto petroleum extracts.

As used herein, “black water” refers to the aqueous side-product fromthe production of bio-oil via the thermochemical conversion of animalwaste. Black water contains nutrients, but no pathogens, and has beenidentified as a useful fertilizer.

As used herein, “bio-char” refers to the insoluble organic materialisolated from the production and post-processing of the bio-oil, asdescribed herein. Typically bio-char contains nutrients, including butnot limited to carbon, metals, sand solid minerals comprising, amongstothers, elements such as nitrogen, phosphorus, potassium, and calcium.As used herein “Light Liquid Fraction” refers to liquid compounds withinbio-oil that have relatively low boiling point at 3 mm mercury (Hg),generally up to 60° C. The Light Liquid Fraction typically containsolefin compounds and is usually an odorous fraction. The molecules inthe fraction include, but are not limited to hexadecanamide,tetradecanal o-methyloxime, and octadecanoic acid. The Light LiquidFraction has applications as sources of energy, including but notlimited to transportation fuel, heating fuel, and use in creatingelectricity, optionally in conjunction with a methane digester.

As used herein “Heavy Liquid Fraction” refers to liquid compounds withinbio-oil that have mid-range boiling points at 3 mm Hg, typically over60° C., generally from 60° C. to 100° C. and from 100° C. to 160° C.These compounds are liquid at room temperature and have adhesioncharacteristics to certain surfaces (substrates). They have apparentdynamic viscosity of up to about 0.5 cP at 135° C., generally betweenabout 0.1 cP and about 0.5 cP. This fraction can have a slight sulfurousodor. The Heavy Liquid Fraction can be isolated as a series ofsub-fractions, for example, a fraction containing hydrocarbons with ahigh concentration of amide groups, for example at least about 5% or atleast about 10%, or at least about 15% by weight amide containingcompounds. Alternately, one Heavy Liquid Fraction contains between about10% and about 20% amide containing compounds. Alternately a Heavy LiquidFraction contains a low concentration of amide groups, for example nomore than about 10% amide-containing compounds or no more than about 5%amide-containing compounds or nor more than about 2% amide containingcompounds. The isolation of these Heavy Liquid sub-Fractions depends onthe isolation methods used, as disclosed herein.

As used herein, “bio-residue” refers to a dark brown to black stickymaterial that is solid at room temperature with penetration gradebetween (25-60) at 25° C. Typically the bio-residue is non-odorous atroom temperature and has a slight sulfurous odor at elevatedtemperatures. Generally bio-residue contains compounds that are highlypolar, have low aromaticity, including some olefinic compounds, andthose with a lower molecular weight.

Generally, the viscosity of the bio-residue is targeted to be less than5.0 cP at 135° C. In one embodiment, the bio-residue has a viscosity ofat least about 0.1 cP, at least about 0.05 cP at 135° C., or at leastabout 0.1 cP; alternately the bio-residue has a viscosity of at leastabout 0.2 cP, at least about 0.3 cP, or at least about 0.4 cP at 135° C.In one variation, the bio-residue has a viscosity of at least 0.5 cP at135° C. In another embodiment, at 135° C. the bio-residue has aviscosity of at least about 0.6 cP, at least about 0.7 cP, at leastabout 0.8 cP, at least about 0.9 cP, at least about 1 cP, or at leastabout 1.5 cP. In yet another embodiment, the bio-residue at 135° C. hasa viscosity of no more than about 2 cP, no more than about 3 cP, no morethan about 4 cP, or no more than about 5 cP. In one alternative, thebio-residue has a viscosity of between about 0.1 cP and about 3 cP at135° C. In another alternative, the bio-residue has a viscosity ofbetween about 0.3 cP and about 2 cP or between about 0.5 and about 1 cPat 135° C.

As used herein, “bio-adhesive” refers to a group of compounds that canbe isolated from bio-oil prepared from animal waste; typicallybio-adhesives have a viscosity between about 0.01 cP and about 5 cP at135° C. In one embodiment, the source of the animal waste is cattle,swine, poultry, sheep or combinations thereof. In another embodiment,the animal waste comprises beef manure, dairy manure, swine manure,sheep manure, poultry manure or combinations thereof. In yet anotherembodiment, the animal waste comprises poultry manure. In anotherembodiment, the animal waste comprises beef or dairy manure. In yetanother embodiment, the animal waste comprises sheep manure. In anotherembodiment, the animal waste comprises swine manure.

In one embodiment, the minimal percentage of animal waste that is solidmanure waste, as opposed to liquid waste, straw, grass etc., is at least2.5% by weight or alternately about 5% by weight. In another embodiment,the percentage of solid manure waste is at least about 10% by weight, atleast about 15%, at least about 20%, at least about 25% or at leastabout 30% by weight. The liquid component of animal waste can be removedor alternately its amount reduced by a variety of methods, including butnot limited to, filtration, centrifugation, condensation, gravimetry andother methods familiar to those of skill in the art for separatingsolids and liquids. In one embodiment, the animal waste is processed bythermochemical liquefaction. In another embodiment, animal waste isprocessed by chemical reactions in presence of a catalyst, including,but not limited to gasification, anaerobic digestion or fast pyrolysis.Alternately, the animal waste is processed though a digester leading toside products, that can be used as a feedstock for the production ofbio-oil, for example a centroid from a methane digester and/or glycerolfrom bio-diesel production

Generally, the viscosity of the bio-adhesive is targeted to be less than5.0 cP at 135° C. In one embodiment, the bio-adhesive has a viscosity ofabout 0.01 cP, about 0.05 cP at 135° C., or about 0.1 cP; alternatelythe bio-adhesive has a viscosity of about 0.2 cP, about 0.3 cP, or about0.4 cP at 135° C. In one variation, the bio-adhesive has a viscosity of0.5 cP at 135° C. In another embodiment, at 135° C. the bio-adhesive hasa viscosity of about 0.6 cP, about 0.7 cP, about 0.8 cP, about 0.9 cP orabout 1 cP. In yet another embodiment, the bio-adhesive at 135° C. has aviscosity of about 2 cP or about 3 cP or about 4 cP or about 5 cP. Inone alternative, the bio-adhesive has a viscosity of between about 0.01cP and about 3 cP at 135° C. In another alternative, the bio-adhesivehas a viscosity of between about 0.01 cP and about 1 cP, between about0.01 cP and about 0.5 cP or between about 0.1 and 0.3 cP at 135° C.Alternately, the bio-adhesive has a viscosity of up to about 1 cP or upto about 0.5 cP or up to about 0.3 cP at 135° C.

As used herein “bio-adhesion promoter” refers to one industrialapplication of a bio-adhesive prepared according to the methods of thepresent application, in which the bio-adhesion promoter improves theinteraction between asphalt and the aggregates comprising asphaltconcrete as disclosed herein. Typically, the bio-adhesion promoter isisolated as part of the Heavy Liquid Fraction. Usually, the bio-adhesionpromoter is comprised of at least about 5% by weight amide containingcompounds. In one embodiment, the bio-adhesion promoter is comprised ofat least about 10% amide containing compounds or at least about 15%amide containing compounds. In another embodiment, the bio-adhesionpromoter is comprised of between about 5% and about 20% amide containingcompounds; alternately, the bio-adhesion promoter is comprised ofbetween about 10 and about 15% amide containing compounds. Generally,the bio-adhesive component with the targeted viscosities and amideconcentrations are combined with bitumen to yield an industrially usefulbio-adhesion promoter. Usually the bio-adhesive component is combined atabout 1% to about 10% by weight with bitumen, for example thebio-adhesive component is combined at about 1% or about 2% or about 3%or about 4% or about 5% or about 6% or about 7% or about 8% or about 9%or about 10% by weight with bitumen.

Typically, a successful bio-adhesion promoter of the present applicationhas a viscosity between about 0.01 cP and about 3 cP at 135° C.Alternately, the bio-adhesion promoter has a viscosity of about 0.01 cP,about 0.05 cP at 135° C., or about 0.1 cP; alternately the bio-adhesionpromoter has a viscosity of about 0.2 cP, about 0.3 cP, about 0.4 cP or0.5 cP at 135° C. In another embodiment, at 135° C. the bio-adhesionpromoter has a viscosity of about 0.6 cP, about 0.7 cP, about 0.8 cP,about 0.9 cP or about 1 cP. In yet another embodiment, the bio-adhesionpromoter at 135° C. has a viscosity of about 2 cP or about 2.5 cP. Inone alternative, the bio-adhesion promoter has a viscosity of betweenabout 0.05 cP and about 2 cP at 135° C. In another alternative, thebio-adhesion promoter has a viscosity of between about 0.1 cP and about1.5 cP or between about 0.1 cP and about 0.5 cP at 135° C. Alternately,the bio-adhesion promoter has a viscosity of up to about 1 cP or up toabout 0.5 cP. Bio-adhesion promoters having the targeted viscosityand/or amide concentration can be prepared according to the methods ofthe present application.

As used herein “asphalt bio-extender” refers to one industrialapplication of a bio-adhesive prepared according to the methods of thepresent application, in which the asphalt bio-extender enables therecycling of asphalt waste, such as RAP or RAS, as well as incorporatingnatural asphalt sources, including but not limited to, rock asphalt, tarsands, Gilsonite, and Trinidad Lake Asphalt. Asphalt bio-extendersgenerally enable a larger amount of asphalt waste material to be used ina performance grade asphalt mix, yielding a product having targetedmechanical and physical properties. Typically, the asphalt bio-extenderis isolated as part of the Heavy Liquid Fraction.

Typically, a successful asphalt bio-extender has a viscosity betweenabout 0.01 cP and about 1 cP at 135° C. Alternately, the asphaltbio-extender has a viscosity of about 0.01 cP, about 0.05 cP at 135° C.,or about 0.1 cP; alternately the asphalt bio-extender has a viscosity ofabout 0.2 cP, about 0.3 cP, about 0.4 cP or 0.5 cP at 135° C. In oneembodiment, at 135° C. the asphalt bio-extender has a viscosity of about0.6 cP, about 0.7 cP, about 0.8 cP, about 0.9 cP or about 1 cP. In yetanother embodiment, the asphalt bio-extender has a viscosity of betweenabout 0.01 cP and about 0.5 cP at 135° C. In another alternative, theasphalt bio-extender has a viscosity of between about 0.1 cP and about0.5 cP or between about 0.2 cP and about 0.5 cP at 135° C. Alternately,the asphalt bio-extender has a viscosity of up to about 1 cP or up toabout 0.5 cP. Asphalt bio-extenders having the targeted viscosity can beprepared according to the methods of the present application.

The asphalt bio-extender disclosed herein is generally combined withasphalt in the refinery, at the blending terminal or some combinationthereof. It can also be introduced to reclaimed asphalt pavement andrecycled asphalt shingles in an amount sufficient to eliminate theadverse stiffening effects of the reclaimed/recycled/asphalt frompavement and/or tear-off and/or manufactured scrap roofing shingles. Thebio-asphalt extender is typically present in an amount of about 5% toabout 75% by weight, or in an amount from about 15% to about 50% byweight, or in an amount from about 10% to about 40% by weight, of thetotal liquid asphalt needed for performance grade asphalt mix. In turn,the amount of liquid asphalt is from about 25% to about 95% of the totalweight of the final performance graded asphalt mix. The amount asphaltwaste material is from about 2% to about 45% of the total weight of theperformance graded asphalt mix; or from about 8% to about 35% of thetotal weight of the performance graded asphalt mix; or from about 10% toabout 25% of the total weight of the performance graded asphalt mix. Theamount of aggregate comprises from about 50% to about 95% of the totalweight of the performance grade asphalt mix, as typically identified inAASHTO standards. The mixing temperature at which asphalt bio-extenderis blended with the asphalt, reclaimed/recycled asphalt, and aggregateis generally from about 80° F. to about 300° F.

As used herein “asphalt bio-rejuvenator” refers to one industrialapplication of the bio-adhesive prepared according to the methods of thepresent application, in which the asphalt bio-rejuvenator is used to forone or more of the following: stops and/or reverses shrinking, inhibitspitting and/or raveling, and reduces air and/or water permeability.Typically, bio-rejuvenator inhibits processes leading to pavementdegradation. Usually, the asphalt bio-rejuvenator is isolated as part ofthe Heavy Liquid Fraction.

Typically, a successful asphalt bio-rejuvenator has a viscosity betweenabout 0.01 cP and about 3 cP at 135° C. Alternately, the bio-rejuvenatorhas a viscosity of about 0.01 cP, about 0.05 cP at 135° C., or about 0.1cP; alternately the bio-rejuvenator has a viscosity of about 0.2 cP,about 0.3 cP, about 0.4 cP or 0.5 cP at 135° C. In another embodiment,at 135° C. the bio-rejuvenator has a viscosity of about 0.6 cP, about0.7 cP, about 0.8 cP, about 0.9 cP or about 1 cP. In yet anotherembodiment, the bio-rejuvenator at 135° C. has a viscosity of about 2 cPor about 2.5 cP. In one alternative, the bio-rejuvenator has a viscosityof between about 0.01 cP and about 3 cP at 135° C. In anotheralternative, the bio-rejuvenator has a viscosity of between about 0.1 cPand about 0.5 cP or between about 0.2 cP and 0.5 cP at 135° C.Alternately, the bio-rejuvenator promoter has a viscosity of up to about1 cP or up to about 0.5 cP at 135° C.

Asphalt bio-rejuvenator having the targeted viscosity can be preparedaccording to the methods of the present application.

As used herein “bitumen” or “asphalt” is the sticky, black and highlyviscous liquid or semi-solid present in most crude petroleum and in somenatural deposits. Asphalt is used in asphalt binders, adhesionpromoters, asphalt rejuvenators, asphalt extenders, as well as asphaltmixtures with nanoclay or rubber. In addition, asphalt can also be usedin roofing, soil stabilization, crack and joint sealing and carpeting asa hot-melt adhesive and to enhance U.V. protection in case of roofing.In such specialty products asphalt has been shown to be an effectivebase material.

As used herein “bio-asphalt” refers to an industrial application of thebio-adhesive prepared according to the methods of the presentapplication, in which the bio-adhesive is used as a stand-alonebio-degradable product having some of the properties of petroleum-basedasphalt, such as viscosity and stickiness. Typically the uses ofbio-asphalt encompass known uses of petroleum-based asphalt, includingbut not limited to roofing, soil stabilization, crack and joint sealing,flooring adhesives and roofing.

Typically the bio-adhesive employed as a bio-asphalt (referred to at 136in FIG. 1A) is isolated from the bio-residue (referred to at 120 in FIG.1A), as represented in FIG. 1A. Generally in this example, a successfulbio-asphalt has a viscosity between about 0.4 cP and about 5 cP at 135°C. Alternately, the bio-asphalt at 135° C. has a viscosity of about 0.5cP, about 1 cP, about 1.5 cP, about 2 cP or about 2.5 cP or about 3 cPor about 3.5 cP or about 4 cP or about 4.5 cP. In one alternative, thebio-asphalt has a viscosity of between about 0.5 cP and about 1 cP at135° C. In another alternative, the bio-asphalt has a viscosity ofbetween about 0.4 cP and about 2.5 cP or about 0.5 cP and about 1.5 cPat 135° C. Alternately, the bio-asphalt has a viscosity of up to about2.5 cP or up to about 1 cP or up to about 0.5 cP at 135° C. Abio-asphalt having the targeted viscosity can be prepared according tothe methods of the present application.

Alternately, the bio-adhesive employed as a bio-asphalt (referred to at136′ in FIG. 1B) is isolated from un-separated combination ofbio-residue and Heavy Liquid Fraction (referred to at 120′ in FIG. 1B),as represented in FIG. 1B. Typically in this example, a successfulbio-asphalt has a viscosity between about 0.1 cP and about 5 cP at 135°C. Alternately, the bio-asphalt has a viscosity of about 0.2 cP, about0.3 cP, about 0.4 cP or 0.5 cP at 135° C. In another embodiment, at 135°C. the bio-asphalt has a viscosity of about 0.6 cP, about 0.7 cP, about0.8 cP, or about 0.9 cP. Alternately, the bio-asphalt at 135° C. has aviscosity of about 1 cP, about 1.5 cP, about 2 cP or about 2.5 cP orabout 3 cP or about 3.5 cP or about 4 cP or about 4.5 cP. In onealternative, the bio-asphalt has a viscosity of between about 0.1 cP andabout 1 cP at 135° C. In another alternative, the bio-asphalt has aviscosity of between about 0.5 cP and about 1 cP at 135° C. In yetanother alternative, the bio-asphalt has a viscosity of between about0.4 cP and about 2.5 cP or about 0.5 cP and about 1.5 cP at 135° C.Alternately, the bio-asphalt has a viscosity of up to about 2.5 cP, upto about 1 cP or up to about 0.5 cP. A bio-asphalt having the targetedviscosity can be prepared according to the methods of the presentapplication.

In one variation, the bio-residue of the present application is usedwithout the addition of any petroleum-based adhesive, generally as abio-asphalt. Alternately, bio-residue of the present applicationoptionally can be combined with modifiers selected from the groupincluding but not limited to nanoclay and rubber. In one variation, thebio-residue is blended with nanoclay to yield a nanoclay-containingbio-asphalt, which is typically a brittle material used in moldingvases, low cost containers, animal feed containers, sport goods, etc. Inanother variation the bio-residue is blended with rubber to yield arubber-containing bio-asphalt, which is typically a flexible materialwith higher strength length. Rubber-containing bio-asphalt hasapplications in sealing cracks and joints, which generally requires highelasticity.

As used herein “asphalt concrete” refers to a composite containingasphalt and aggregate, prepared using standard methods, including warmmix, semi-cold mix, cold mix, and hot mix asphalt technologies.

The term “aggregate” refers to materials such as stone aggregate,crushed stone, tar sands, slag, natural sand, stone sand, stone dust,soil, or similar materials. Aggregate can optionally further contain andrubber-based material, including but not limited to ground rubber, crumbrubber, virgin rubber, or similar materials.

The phrase “asphalt binder” or “petroleum binder,” as used herein isgenerally consistent with the meaning provided by AASHTO M320 or ASTMD-6373. The asphalt binder material may be derived from any asphaltsource, such as natural asphalt, rock asphalt, produced from tar sands,or petroleum-based asphalt. The asphalt binder may be selected fromthose currently graded by AASHTO M320 and ASTM D-6373, includingPerformance Graded Asphalt Binders.

As used herein, a “binder mixture” may contain a petroleum-based asphaltbinder, a polymer-based asphalt binder additive, or combinationsthereof. Asphalt binders may further include a blend of various asphaltsnot meeting any specific grade definition, including air-blown asphalt,vacuum-distilled asphalt, steam-distilled asphalt, cutback asphalt orroofing asphalt. Alternatively, synthetic binders, such as gilsonite(natural or synthetic) can be used alone or mixed with petroleum asphaltas a binder. When asphalt binder mixtures contain a bio-adhesiveprepared according to the methods of the present application, suchmixtures are typically referred to as “bio-modified asphalt mixtures”(BMAM).

As used herein “bio-binder” refers to an industrial application of thebio-adhesive prepared according to the methods of the presentapplication, in which the bio-adhesive has a minimum viscosity of about0.3 cP at 135° C., usually a measured viscosity of about 0.5 cP at 135°C. Typically the bio-residue (referred to at 120 in FIG. 1A) frombio-oil (referred to at 106 in FIG. 1A) is employed as a bio-binder((referred to at 134 in FIG. 1A)), in which the viscosity is at leastabout 0.5 cP at 135° C. Alternately, according to another variation inthe current application, the Heavy Liquid Fraction and the bio-residue(referred to at 120′ in FIG. 1B) are not fully separated inpost-processing and the mixture of components is employed as abio-binder ((referred to at 134′ in FIG. 1B)), in which the viscosity isbetween about 0.1 cP and about 5 cP at 135° C. In another variation, theviscosity is up to about 2.5 cP or up to about 1 cP or up to about 0.5cP.

Typically the bio-adhesive employed as a bio-binder (referred to at 134in FIG. 1A) is isolated from the bio-residue (referred to at 120 in FIG.1A), as represented in FIG. 1A. Generally in this example, a successfulbio-binder has a viscosity between about 0.5 cP and about 5 cP at 135°C. Alternately, the bio-binder at 135° C. has a viscosity of about 1 cP,about 1.5 cP, about 2 cP or about 2.5 cP or about 3 cP or about 3.5 cPor about 4 cP or about 4.5 cP. In one alternative, the bio-binder has aviscosity of between about 0.5 cP and about 1 cP at 135° C. In anotheralternative, the bio-binder has a viscosity of between about 0.4 cP andabout 2.5 cP or about 0.5 cP and about 1.5 cP at 135° C. In yet anotheralternative, the bio-binder has a viscosity of between about 0.5 cP andabout 0.75 cP at 135° C. Alternately, the bio-binder has a viscosity ofup to about 2.5 cP, up to about 1 cP or up to about 0.5 cP at 135° C. Abio-binder having the targeted viscosity can be prepared according tothe methods of the present application.

Alternately, the bio-adhesive employed as a bio-binder (referred to at134′ in FIG. 1A) is isolated from unseparated combination of bio-residueand Heavy Liquid Fraction (referred to at 120′ in FIG. 1A), asrepresented in FIG. 1B. Typically in this example, a successfulbio-binder has a viscosity between about 0.1 cP and about 5 cP at 135°C. Alternately, the bio-binder has a viscosity of about 0.2 cP, about0.3 cP, about 0.4 cP or 0.5 cP at 135° C. In another embodiment, at 135°C. the bio-binder has a viscosity of about 0.6 cP, about 0.7 cP, about0.8 cP, or about 0.9 cP. Alternately, the bio-binder at 135° C. has aviscosity of about 1 cP, about 1.5 cP, about 2 cP or about 2.5 cP orabout 3 cP or about 3.5 cP or about 4 cP or about 4.5 cP. In onealternative, the bio-binder has a viscosity of between about 0.1 cP andabout 1 cP at 135° C. In another alternative, the bio-binder has aviscosity of between about 0.3 cP and about 0.8 cP at 135° C.Alternately, the bio-binder has a viscosity of up to about 2.5 cP, up toabout 0.8 cP or up to about 0.5 cP. A bio-binder having the targetedviscosity can be prepared according to the methods of the presentapplication.

As used herein, “bio-modified binder” (BMB) refers to an asphalt bindercombined with the bio-binder of the present application. In oneembodiment the BMB comprises at least about 2% by weight bio-binder. Inanother embodiment the bio-binder is combined with asphalt binder up toabout 50% by weight of the final BMB, alternately at between about 2%and about 50% by weight of the final BMB. In one variation, the BMBcomprises between about 5% and about 45%, between about 10% and about40%, between about 15% and about 35%, or between about 20% and about 30%bio-binder.

In one variation, the BMB comprises at least about 2% or at least about5% or at least about 10% or at least about 15% or at least about 20% orat least about 25% or at least about 30% or at least about 35% or atleast about 40% or at least about 45% or at least about 50% bio-binder.

Asphalt binders, prior to combination with bio-binder, can becharacterized by their temperature performance range, which is usually86° C. Familiar to those of skill in the art, PG rating refers to SuperPave (Superior Performing Pavements) Performance Graded (PG) binderspecifications as developed in the United States through research fundedby the Association of American Highway and Transportation Officials(AASHTO M320). PG ratings, e.g. PG 64-22, are identified by a firstnumber, (64) which is equivalent to the maximum 7 day temperature (in °C.) for which the binder is tested; the second number (−22) is theminimum temperature (in ° C.) at which cracking caused by lowtemperatures is not observed. Typically, commercial asphalt binders havea PG rating of PG 64-22, PG 52-28, or PG 52-34, etc. Combiningcommercial and non-commercial asphalt binders with the bio-binder of thepresent application leads to a bio-modified binder, which iseco-friendly and has a broader PG range and/or allows asphalt bindershaving a broader temperature performance range to be industriallyuseful. For example, a BMB containing PG 64-28 (with 92° C. usefultemperature interval) can be prepared by blending BMB with PG 64-22(with 86° C. useful temperature interval).

As used herein, “RAP” refers to Reclaimed Asphalt Pavements, the termtypically given to removed and reprocessed pavement materials containingasphalt and aggregates. RAP generally contains 3%-7% asphalt by weight.RAP is usually used in surface asphalt mixtures at no more than 20%, dueto limitations on the resulting asphalt quality. Without being bound bytheory, it is believed that the aged binder in RAP is one of the factorsleading to increased mixture stiffness. Addition of BMB can facilitateblending of the aged binder in RAP and virgin binder allowing forintroduction of about 20%-30% higher RAP into the mixture, so forexample the amount of RAP used in surface asphalt mixtures comprisingbio-binder can range from about 20% up to about 50%. The percent of RAPin the mixture can be at least about 25%, at least about 30%, at leastabout 35%, at least about 40%, at least about 45% or at least about 50%of the overall surface asphalt mixture.

As used herein “RAS” refers to recycled asphalt shingles. RAS aregenerally composed of 30%-35% asphalt cement by weight. RAS is usuallyused in surface asphalt mixtures at no more than 5%, due to limitationson the resulting asphalt quality. Without being bound by theory, it isbelieve that the aged binder in RAS is one of the factors leading toincreased mixture stiffness, analogous to aged RAP. Addition of BMB canfacilitate blending of the aged binder in RAS and virgin binder allowingfor introduction of about 10%-15% higher RAS into the mixture, so forexample the amount of RAS used in surface asphalt mixtures comprisingbio-binder can range from about 5% up to about 20%. The percent of RASin the mixture can be at least about 10%, at least about 15%, or atleast about 20% of the overall surface asphalt mixture.

“Rubber” as used herein generally refers to recycled rubber, but canalso include proportions of virgin rubber. A typical, but not exclusive,source of recycled rubber is used tires.

The present application generally discloses a method of vacuumdistillation that can separate industrially useful fractions of bio-oilwhile controlling the viscosity of the resulting commercially relevantresidue.

As disclosed herein, and referring to FIGS. 1A and 1B, process flows forconverting animal waste are referred to generally as 100 and 100′. Inprocesses 100 and 100′ animal waste 102 can be converted to bio-oil 106using methods known to those of skill in the art, including, but notlimited to thermochemical liquefaction and catalyzed chemicalmodification, referred to at 104 in FIGS. 1A and 1B. The resultingbio-oil 106 can then be processed according to processes 100 and 100′ toproduce a variety of industrially useful components, including but notlimited to: bio-char 114, a light liquid component 116, a heavy liquidcomponent 118, and a bio-adhesive residue 120. In one variation, theprocessing of bio-oil 106 comprises adding a solvent, such as acetone oran acetone/toluene mix to the product of the thermochemicalliquefaction, a mixture of bio-char+bio-oil and transferring to mixtureto a filtration device (all of which are referred to schematically at112 and 112′ in FIGS. 1A and 1B), which separates out the insolublebio-char 114 and 114′. The bio-oil 106 in solution is transferred to avacuum distillation apparatus (referred to schematically at 112 and 112′in FIGS. 1A and 1B and at 206 in FIG. 2). The apparatus is set to apressure of between about 1 mm Hg and about 80 mm Hg. Alternately thepressure of the apparatus can be set to at least about 1 mm Hg, at leastabout 2 mm Hg, at least about 3 mm Hg, at least about 4 mm Hg, at leastabout 5 mm Hg, at least about 6 mm Hg, at least about 7 mm Hg, at leastabout 8 mm Hg, at least about 9 mm Hg or at least about 10 mm Hg. Inanother variation the pressure of the apparatus can be set to no morethan about 20 mm Hg, no more than about 30 mm Hg, no more than about 40mm Hg, no more than about 50 mm Hg, no more than about 60 mm Hg, no morethan about 70 mm Hg or no more than about 80 mm Hg. In anothervariation, the apparatus is heated at a rate of between about 5° C. perhour and about 50° C. per hour to a final temperature of between about130° C. and about 250° C. In one variation, the heating rate is betweenabout 10° C. per hour and about 45° C. per hour, alternately betweenabout 15° C. per hour and about 40° C. per hour, or between about 20° C.per hour and about 35° C. per hour, or between about 25° C. per hour andabout 30° C. per hour. In another variation, the heating rate is no morethan about 5° C. per hour, no more than about 10° C. per hour, no morethan about 15° C. per hour, no more than about 20° C. per hour, no morethan about 25° C. per hour, no more than about 30° C. per hour, no morethan about 35° C. per hour, no more than about 40° C. per hour, no morethan about 45° C. per hour or no more than about 50° C. per hour. In onevariation, the temperature is not raised above about 130° C., or aboveabout 140° C., or above about 150° C., or above about 160° C., or aboveabout 170° C., or above about 180° C., or above about 190° C., or aboveabout 200° C., or above about 210° C., or above about 220° C., or aboveabout 230° C., or above about 240° C., or above about 250° C. In oneembodiment, the pressure range is between about 1 mm Hg and about 5 mmHg and the temperature heating rate is no more than about 30° C. perhour to a final temperature of no more than about 160° C., alternatelyto a final temperature of no more than about 100° C. In anotherembodiment, the pressure range is between about 2 mm Hg and about 10 mmHg and the heating rate is no more than about 15° C. per hour to a finaltemperature of not more than about 170° C., alternately to a finaltemperature of no more than about 130° C. In another embodiment, thepressure range is between about 5 mm Hg and about 15 mm Hg and theheating rate is no more than about 10° C. per hour to a finaltemperature of not more than about 180° C., alternately to a finaltemperature of not more than about 150° C. In another embodiment, thepressure range is between about 10 mm Hg and about 30 mm Hg and theheating rate is no more than about 10° C. per hour to a finaltemperature of not more than about 170° C., alternately to a finaltemperature of not more than about 160° C. In another embodiment, thepressure range is between about 30 mm Hg and about 50 mm Hg and theheating rate is no more than about 10° C. per hour to a finaltemperature of not more than about 160° C. In another embodiment, thepressure range is between about 50 mm Hg and about 70 mm Hg and theheating rate is no more than about 10° C. per hour to a finaltemperature of not more than about 180° C. In one variation of any ofthe disclosed embodiments, the heating rate is no more than about 5° C.per hour.

Typically, the viscosity of the bio-adhesive composition remaining inthe distillation pot is monitored on a regular basis. For example, theviscosity of the bio-adhesive composition can be monitored every 30minutes, every 20 minutes, every 10 minutes or every 5 minutes.Alternately, the viscosity of the bio-adhesive composition can bemeasured continuously. Using methods known to those of skill in the art,viscosity can be determined by removing small samples from thedistillation pot, or alternately, the distillation pot can be adapted tomeasure viscosity in situ, e.g. the viscosity can be measured bydetermining the torque necessary to stir the pot liquor.

In one aspect, the present application discloses a method of isolating abio-adhesive composition from a bio-oil, the method comprising: (a)providing a bio-oil derived from animal waste; (b) distilling thebio-oil to remove a light liquid fraction, wherein the distilling occursat a vacuum pressure of between about 1 mm Hg and about 80 mm Hg whileheating to a temperature of up to about 60° C., optionally wherein therate of the heating is between about 5° C. per hour and about 50° C. perhour; and (c) isolating a bio-adhesive composition from the bio-oilunder conditions such that the viscosity of the bio-adhesive compositionis not allowed to exceed about 1 centipoise (cP) at 135° C., optionallywherein the viscosity of the bio-adhesive composition is not allowed toexceed about 0.5 cP at 135° C. In one variation, the bio-adhesivecomposition comprises a heavy liquid fraction and a bio-residue. Inanother variation, the method further comprises using the bio-adhesivecomposition as a component of a composition selected from the groupconsisting of a bio-adhesion promoter, an asphalt bio-extender, abio-rejuvenator, a biomodified binder, and a bio-asphalt, wherein thebio-asphalt is optionally a rubber-containing bio-asphalt or ananoclay-containing bio-asphalt.

In another aspect, the present application discloses a method ofisolating a bio-adhesive composition from a bio-oil, the methodcomprising: (a) providing a bio-oil derived from animal waste; (b)distilling the bio-oil to provide a distilled heavy liquid fraction anda bio-residue that is not distilled, wherein the distilling occurs undervacuum pressure, optionally of between about 1 mm Hg and about 80 mm Hg,while heating to (1) a temperature ranging from about 60° C. to about100° C., or (2) a temperature ranging from about 100° C. to about 160°C., wherein the viscosity of the bio-residue is not allowed to exceedabout 1 cP at 135° C., optionally wherein the viscosity of thebio-residue is not allowed to exceed about 0.5 cP at 135° C. and furtheroptionally wherein the rate of the heating is between about 5° C. perhour and about 50° C. per hour; and (c) isolating the bio-adhesivecomposition comprising the heavy liquid fraction.

In one variation of any disclosed aspect or embodiment, the methodfurther comprises isolating a bio-adhesive composition comprising thebio-residue. In embodiment, the animal waste comprises beef manure,dairy manure, swine manure, sheep manure, poultry manure or combinationsthereof. In another variation, the temperature ranges from about 60° C.to about 100° C. and the bio-adhesive composition comprises a heavyliquid fraction comprising at least about 5% by weight ofamide-containing compounds, optionally wherein the composition comprisesa heavy liquid fraction comprising between about 10% and about 20% byweight of amide-containing compounds. In another variation, thetemperature ranges from 100° C. to 160° C. and the bio-adhesivecomposition comprises a heavy liquid fraction comprising up to about 5%by weight of amide-containing compounds, optionally wherein thecomposition comprises a heavy liquid fraction comprising between about1% and about 5% by weight of amide-containing compounds. In oneembodiment, the method further comprises distilling the bio-oil toremove a light liquid fraction, wherein the distilling occurs at vacuumpressure between about 1 mm Hg and about 80 mm Hg while heating atemperature of up to 60° C., optionally wherein the rate of the heatingis between about 5° C. per hour and about 50° C. per hour. In anotherembodiment, the animal waste comprises swine manure and the vacuumpressure is between about 1 mm and about 40 mm Hg, optionally whereinthe vacuum pressure is between about 1 mm and about 10 mm Hg. In yetanother embodiment, the bio-oil is treated with a solvent to provide abio-char, optionally, wherein the bio-char is isolated by filtration. Inone variation, the method further comprises using the bio-adhesivecomposition as a component of a composition selected from the groupconsisting of a bio-adhesion promoter, an asphalt bio-extender, and abio-rejuvenator. In another variation, the method further comprisesusing the bio-adhesive composition comprising the bio-residue as acomponent of a composition selected from the group consisting of abio-modified binder and a bio-asphalt, wherein the bio-asphalt isoptionally a rubber-containing bio-asphalt or a nanoclay-containingbio-asphalt.

The present application discloses a bio-adhesive composition produced byany of the methods disclosed herein.

In one aspect, the present application discloses a bio-adhesivecomposition comprising a heavy liquid fraction and a bio-residue,wherein the composition has a viscosity of at least about 0.5 cP at 135°C., optionally between about 0.5 cP and about 1 cP at 135° C. whereinsaid heavy liquid fraction and bio-residue are isolated from bio-oilproduced from animal waste and wherein said bio-adhesive compositiondoes not contain a light liquid fraction.

In another aspect, the present application discloses a bio-adhesivecomposition comprising a heavy liquid fraction having a viscosity ofbetween about 0.1 cP and 0.5 cP at 135° C., optionally, between about0.2 cP and about 0.5 cP, wherein said bio-adhesive composition does notcontain a light liquid fraction and wherein said heavy liquid fractionis isolated from bio-oil produced from animal waste.

In one embodiment, the present application discloses a bio-adhesivecomposition comprising (a) a heavy liquid fraction comprising at leastabout 5% by weight of amide-containing compounds, optionally containingabout 10% to about 20% by weight of amide-containing compounds, or (b) aheavy liquid fraction comprising up to about 5% by weight ofamide-containing compounds, optionally about 1% to about 5% by weight ofamide-containing compounds, wherein said bio-adhesive composition doesnot contain a light liquid fraction.

In another aspect, the present application discloses a bio-adhesivecomposition comprising a bio-residue having a viscosity of at leastabout 0.4 cP, optionally between about 0.5 cP and 1 cP, at 135° C.,wherein said bio-adhesive composition does not contain a light liquidfraction and wherein said bio-residue is isolated from bio-oil producedfrom animal waste.

In yet another aspect, the present application discloses a bio-adhesionpromoter comprising a bio-adhesive composition of the presentapplication, optionally wherein the bio-adhesive composition comprisesat least about 5% by weight amide-containing compounds. The presentapplication also discloses a method of making bio-modified asphaltcomposition comprising contacting components for an asphalt compositionwith a bio-adhesion promoter disclosed herein.

In yet another aspect, the present application discloses an asphaltbio-extender comprising a bio-adhesive composition disclosed herein, andoptionally an asphalt binder. In another aspect, the present applicationdiscloses a method of making a bio-modified asphalt compositioncomprising contacting components for an asphalt composition with anasphalt bio-extender of the present application.

In a further aspect, the present application discloses a bio-rejuvenatorfor asphalt compositions comprising a bio-adhesive composition asdisclosed herein and optionally an asphalt binder. In another aspect,the present application discloses a method of rejuvenating asphaltpavement, comprising contacting an asphalt composition with abio-rejuvenator as disclosed herein.

In another aspect, the present application discloses a bio-modifiedbinder comprising a bio-adhesive composition disclosed herein. Thepresent application also discloses a bio-modified composition comprisinga bio-adhesive composition of the present application and optionallyasphalt, and further optionally wherein the asphalt is recycled asphalt.In another aspect, the present application also discloses arubber-containing bio-asphalt composition comprising a bio-adhesivecomposition disclosed herein, rubber and optionally comprising anasphalt binder and/or an aggregate other than rubber. In a furtheraspect, the present application further discloses a nanoclay-containingbio-asphalt comprising a bio-adhesive composition as disclosed herein,nanoclay and optionally comprising an asphalt binder and/or an aggregateother than nanoclay.

The present application also discloses a method of covering a surfacewith a bio-modified asphalt composition, comprising contacting thesurface with such a composition, optionally wherein the surface is aroof, a road, a floor, a crack or a joint. Further, the presentapplication discloses a method of sealing a crack or joint in asphaltpavement comprising applying a bio-modified composition as disclosedherein.

In one aspect, the present application discloses a method of isolating abio-adhesive composition from a bio-oil, the method comprising: (a)providing a bio-oil derived from animal waste; (b) distilling thebio-oil to remove a light liquid fraction, wherein the distilling occursat a vacuum pressure of between about 1 mm Hg and about 80 mm Hg whileheating at a rate of between about 5° C. per hour and about 50° C. to atemperature of up to 60° C.; and (c) isolating a bio-adhesivecomposition from the bio-oil under conditions such that the viscosity ofthe bio-adhesive composition is not allowed to exceed 1 centipoise (cP)at 135° C. In one embodiment, the animal waste comprises beef manure,dairy manure, swine manure, sheep manure, poultry manure or combinationsthereof; in one variation, the animal waste comprises swine manure. Inanother variation, the animal waste consists essentially of swine waste.In another embodiment, the viscosity of the bio-adhesive composition isnot allowed to exceed 0.5 cP at 135° C. In another embodiment, thebio-adhesive composition comprises a heavy liquid fraction and abio-residue. In one variation of any of the disclosed aspects orembodiments, the vacuum pressure is about 3 mm Hg. In another variation,the bio-oil is treated with a solvent to provide a bio-char; in onealternative, the bio-char is isolated by filtration. In anotherembodiment, the method further comprises using the bio-adhesivecomposition as a component of a composition selected from the groupconsisting of a bio-adhesion promoter, an asphalt bio-extender, abio-rejuvenator, a biomodified binder, and a bio-asphalt. In onevariation, the bio-asphalt is a rubber-containing bio-asphalt or ananoclay-containing bio-asphalt.

In another aspect, the present application discloses a method ofisolating a bio-adhesive composition from a bio-oil, the methodcomprising: (a) providing a bio-oil derived from animal waste; (b)distilling the bio-oil to provide a distilled heavy liquid fraction anda bio-residue that is not distilled, wherein the distilling occurs undervacuum pressure while heating at a rate of between about 5° C. per hourand about 50° C. per hour to (1) a temperature ranging from 60° C. to100° C., or (2) a temperature ranging from 100° C. to 160° C., whereinthe viscosity of the bio-residue is not allowed to exceed 1 cP at 135°C.; and (c) isolating the bio-adhesive composition comprising the heavyliquid fraction. In one embodiment, the method further comprisesisolating a bio-adhesive composition comprising the bio-residue. In onevariation of any disclosed aspect or embodiment, the animal wastecomprises beef manure, dairy manure, swine manure, sheep manure, poultrymanure or combinations thereof. In one alternative, the animal wastecomprises swine manure; in another variation, the animal waste consistsessentially of swine waste. In another variation, the viscosity of thebio-residue is not allowed to exceed 0.5 cP at 135° C. In one embodimentof the methods disclosed herein, the temperature ranges from 60° C. to100° C. and the bio-adhesive composition comprises a heavy liquidfraction comprising about 10% to about 20% by weight of amide-containingcompounds. In another embodiment of the disclosed methods, thetemperature ranges from 100° C. to 160° C. and the bio-adhesivecomposition comprises a heavy liquid fraction comprising about 1% toabout 5% by weight of amide-containing compounds. In one variation, themethods disclosed herein further comprise distilling the bio-oil toremove a light liquid fraction, wherein the distilling occurs at vacuumpressure between about 1 mm Hg and about 80 mm Hg while heating at arate of between about 5° C. per hour and about 50° C. to a temperatureof up to 60° C. In yet another variation, the vacuum pressure is about 3mm Hg. In one embodiment, the bio-oil is treated with a solvent toprovide a bio-char; in one variation, the bio-char is isolated byfiltration. In one embodiment, the method further comprises using thebio-adhesive composition as a component of a composition selected fromthe group consisting of a bio-adhesion promoter, an asphaltbio-extender, and a bio-rejuvenator. In another embodiment, the methodfurther comprises using the bio-adhesive composition comprising thebio-residue as a component of a composition selected from the groupconsisting of a bio-modified binder and a bio-asphalt. In one variation,the bio-asphalt is a rubber-containing bio-asphalt or ananoclay-containing bio-asphalt.

In one aspect, the present application discloses a bio-adhesivecomposition produced by any of the methods disclosed herein. In anotheraspect, the present application discloses a bio-adhesive composition,comprising a heavy liquid fraction and a bio-residue, wherein thecomposition has a viscosity of about 0.5 cP at 135° C. wherein saidheavy liquid fraction and bio-residue is isolated from bio-oil producedfrom animal waste and wherein said bio-adhesive composition does notcontain a light liquid fraction. In yet another aspect, the presentapplication discloses a bio-adhesive composition, comprising a heavyliquid fraction having a viscosity of between about 0.1 cP and 0.5 cP at135° C., optionally, between about 0.2 cP and about 0.5 cP, wherein saidbio-adhesive composition does not contain a light liquid fraction. Inone variation of any of the disclosed aspects or embodiments, thebio-adhesive composition comprises a heavy liquid fraction comprisingabout 10% to about 20% by weight of amide-containing compounds, whereinsaid bio-adhesive composition does not contain a light liquid fraction.In another variation, the bio-adhesive composition comprises a heavyliquid fraction comprising about 1% to about 5% by weight ofamide-containing compounds, wherein said bio-adhesive composition doesnot contain a light liquid fraction.

In another aspect, the present application discloses a bio-adhesivecomposition, comprising a bio-residue having a viscosity of at leastabout 0.4 cP, optionally between about 0.5 cP and 1 cP, at 135° C.,wherein said bio-adhesive composition does not contain a light liquidfraction.

In yet another aspect, the present application discloses a bio-adhesionpromoter comprising any bio-adhesive composition disclosed herein. Inone embodiment, the bio-adhesive composition comprises at least about 5%by weight amide containing compounds. In one embodiment, the presentapplication discloses a method of making bio-modified asphaltcomposition, comprising contacting components for an asphalt compositionwith a bio-adhesion promoter disclosed herein.

In another aspect, the present application discloses an asphaltbio-extender comprising a bio-adhesive composition disclosed herein andoptionally an asphalt binder. In one embodiment, the present applicationdiscloses a method of making a bio-modified asphalt composition,comprising contacting components for an asphalt composition with anasphalt bio-extender disclosed herein.

In yet another aspect, the present application discloses abio-rejuvenator for asphalt compositions, the bio-rejuvenator comprisinga bio-adhesive composition as disclosed herein, and optionally anasphalt binder. In one embodiment, the application discloses a method ofrejuvenating asphalt pavement, comprising contacting an asphaltcomposition with a bio-rejuvenator disclosed herein.

In another aspect, the present application discloses a bio-modifiedbinder comprising a bio-adhesive composition disclosed herein andoptionally asphalt. In one variation of any of the disclosed aspects orembodiments, the asphalt in the bio-modified composition is recycledasphalt. In another aspect, the present application discloses arubber-containing bio-asphalt composition comprising a bio-adhesivecomposition disclosed herein, rubber and optionally an asphalt binder.In yet another aspect, the present application discloses ananoclay-containing bio-asphalt comprising a bio-adhesive compositiondisclosed herein, nanoclay and optionally an asphalt binder. In onevariation of any of the disclosed aspects or embodiments, thebio-modified asphalt composition further comprises an aggregate otherthan rubber or nanoclay. In one aspect the present application disclosesa method of covering a surface with a bio-modified asphalt composition,comprising contacting the surface with a composition disclosed herein.In one variation, the surface is a roof, a road, a floor, a crack or ajoint. In another aspect, the present application discloses a method ofsealing a crack or joint in asphalt pavement comprising applying abio-modified composition as disclosed herein.

Depending on the properties of the components targeted and isolatedaccording to the methods of the present application as disclosed herein,a range of industrially useful products can be prepared including, butnot limited to, a fertilizer nutrient, bio-soil amendment, bio-fuels, abio-adhesion promoter, an asphalt bio-extender, an asphalt bio-binderand a bio-asphalt.

EXAMPLES

Materials and Methods

Preparation of Bio-Oil

Bio-oil can be obtained from animal waste according to methods known tothose of skill in the art, including thermochemical liquefaction(“TCC”), a chemical reforming process using heat and pressure in theabsence of oxygen to break down long-chain organic compounds into shortchain molecules yielding a bio-oil. For example, swine manure can beconverted to bio-oil via TCC under known conditions, for example at 305°C. at 10.3 MPa at a residual time of 80 minutes (Ocfemia, K., 2005“Hydrothermal Process of Swine Manure to Oil Using a Continuous ReactorSystem” Dissertation, University of Illinois at Urbana-Champaign, AAT3202149).

Beef, dairy, or poultry manure can be converted to bio-oil viathermochemical liquefaction under known conditions, for example at 350°C., with 15 minute retention time, using CO as process gas, at apressure of 2.06 MPa, with the addition of 1 g sodium carbonate.(Midgett, J. S. 2008 “Assessing A Hydrothermal Liquefaction ProcessUsing Biomass Feedstocks” Thesis, Louisiana State University).

In the following examples, thermochemical liquefaction of animal wasteto form bio-oil was conducted using a high-pressure batch reactor(autoclave). The experimental set-up is rated up to a working pressureof 34.4 MPa and a working temperature of 500° C. A heavy-duty magneticdrive stirrer was used for mixing. A type-J thermocouple was fitted intothe reactor for direct temperature measurements of the reaction media. Astandard pressure gauge was used on the reactor head. A temperaturecontroller was used to control the temperature of the reactor.

Example 1a. Preparation of Bio-Oil From Chicken Manure

Chicken manure slurry retrieved from NC A&T's farm (Greensboro, N.C.,United States of America) was employed. About 1 gallon of chicken manureslurry, which is typically about 60-80% liquid by weight, was charged ina 1.5 gallon reactor. Nitrogen gas was used to purge the reactor threetimes.

The purged reactor was then heated over the course of ˜2.5 hours to asetting temperature of 340° C., and the pressure of the autoclave raisedto a reaction pressure of about 10.3 MPa. The setting temperature canalternately be set to between about 280° C. and about 360° C. When runat 340° C. at 10.3 MPa, the reaction was completed in about 15-20minutes. The reactor was cooled to room temperature using a recycledice-water cooling coil over the course of at least about 2 hours. Aftercooling, the by-product gas was released from the autoclave, and thepressure in the autoclave reduced to atmospheric pressure.

The reaction mixture, including bio-oil, solid and aqueous phases, canbe removed from the autoclave for subsequent processing and separationas in Example 2.

Example 1b. Preparation of Bio-Oil From Swine Manure

Swine manure slurry retrieved from lagoons or deep pits on NC A&T's farmwas employed in the following procedure.

About 1 gallon of swine manure slurry, which is typically about 80%-95%liquid by weight, was charged in a 1.5 gallon reactor. Nitrogen gas wasused to purge the reactor three times as an optional step; alternately,the thermochemical liquefaction can be run in a semi-closed system,wherein the gaseous reaction products pressurize the reaction container,thereby decreasing the concentration of oxygen to negligible levels. Thepurged reactor was then heated over the course of ˜2.5 hours to asetting temperature of 340° C., and the pressure of the autoclave raisedto a reaction pressure of 10.3 MPa. The setting temperature canalternately be set to between about 280° C. and about 360° C. When runat 340° C. at 10.3 MPa, the reaction was completed in about 15 minutes.The reactor was cooled to room temperature using a recycled ice-watercooling coil over the course of at least about 2 hours. After cooling,the by-product gas was released from the autoclave, and the pressure inthe autoclave reduced to atmospheric pressure.

The reaction mixture, including bio-oil, solid and aqueous phases, wasremoved from the vessel for separation as in Example 2.

Example 2: Isolation of Components From Bio-Oil Produced From SwineManure

Generally, the components of the bio-oil were isolated via a step-wiseprocess: The aqueous phase was isolated via filtration as ‘black water.’The solid by-product was isolated by adding solvent (acetone oracetone/toluene mixture) to the sticky residue thereby dissolving thebio-oil and leaving behind insoluble bio-char, comprising roughly 10% ofthe bio-oil. The bio-oil+solvent was then vacuum distilled at 3 mm Hgwith heating at a rate of between 15° C. per hour and 30° C. per hour upto final distillation temperature of about 160° C. The variousfractions, including solvent, light liquid fraction and the remainingmixture of a heavy liquid fraction and bio-residue were isolated asdescribed.

Example 2a: Isolation of Black Water From Bio-Oil

The reaction mixture, including bio-oil, solid and aqueous phases, fromExample 1b was vacuum filtered. The filtrate, referred to as blackwater, was isolated and can be used as a soil fertilizer, as it is richin agricultural nutrients and does not contain measureable amounts ofpathogens.

Example 2b: Isolation of Bio-Char From Bio-Oil

The sticky residue from the vacuum filtration of Example 2a was rinsedwith 10-50% solvent (either acetone or a 30:70 acetone/toluene mixture)and filtered.

The solid by-product isolated from the filtration, referred to as“bio-char” generally comprises about 10% of intermediate bio-oil byweight and can be used in soil amendment.

Example 2c: Isolation of Light Liquid Component From Bio-Oil

The filtrate from Example 2b was placed in a vacuum distillationapparatus and the pressure in the apparatus was lowered to 3 mm Hg.

The gaseous fractions of the bio-oil, the solvent (acetone oracetone/toluene mix) and the Light Liquid Fraction were collected viavacuum distillation at 3 mm Hg up to a distillation temperature of 60°C., using a heating rate of 15° C.-30° C. per hour.

To obtain gasoline and other liquid fuels, the quality of the lightliquid component from the bio-oil of the present application can beenimproved by using processes such as fractional distillation, thermalcracking, hydrogenation and/or other methods familiar to those of skillin the art.

Example 2d: Isolation of Bio-Residue and Heavy Liquid Fraction(“Bio-Residue+HLF”)

After removal of the gaseous components, the solvent and the lightliquid fraction, the remaining pot liquor from Example 2c comprised aheavy liquid fraction and bio-residue. The viscosity of the remainingmixture was measured every 10 minutes during distillation of the LightLiquid Fraction and the viscosity was not allowed to go above 0.5 cP at135° C. before the mixture was removed from the apparatus and isolated.

Example A. Preparation of a Bio-Adhesion Promoter

It has been shown that the bio-adhesive sample from Example 2d hasproperties of a bio-adhesion promoter. In particular, the Example 2dsample was combined with petroleum-based asphalt binder at a proportionof 5%:95% (bio-product: petroleum product) and the resultingbio-modified binder mixture was then combined with quartz substrate andsubjected to a direct adhesion test (conditioning in water at 25° C. for1 hr. or 8 hr.). The results in FIG. 3 demonstrate the higher adhesionstrength for the bio-modified sample.

Without being bound by theory, it is believed that the bio-adhesives ofthe present application, such as for example, the heavy liquid fractionwith amide-containing compounds, have polar ends and a non-polarhydrocarbon tails. When the bio-adhesive is added to a petroleum-basedasphalt binder, the polar ends of the compounds in the bio-adhesiveattach to the aggregates, such as quartz substrate (polar surfaces) andthe non-polar tails attach to asphalt (non-polar), thereby promotingadhesion between asphalt and quartz substrate.

Example B. Preparation of an Asphalt Bio-Extender

It has been shown that the bio-adhesive sample from Example 2d hasproperties of an asphalt bio-extender. In particular, the bio-adhesivesample from Example 2d, having a viscosity of 0.5 cP at 135° C. wasadded to asphalt base binder PG 64-22 at 2%, 5%, and 10% by weight ofthe base binder to produce bio-modified binder. Bio-binder and basebinder were heated to 60° C. and 120° C., respectively. The base binderand bio-binder were mixed thoroughly at shear rate of 3000 rpm for 30minutes, while the temperature was kept at 120° C.

The asphalt and bio-modified asphalt samples were evaluated using abending beam rheometer (BBR), which measures stiffness and creep rate attemperatures representative of the lowest pavement temperature. In theexperiment, a constant load is applied at the center of an asphaltsample for four minutes—the load simulates the stresses that build up inpavement upon a drop in temperature. The m-value, as determined by BBRis a measure of how the asphalt stiffness changes as loads are appliedand is the slope of log stiffness versus log time curve at any time, t.

As shown in FIG. 4, the m-value of virgin asphalt increases due to theaddition of bio-binder, improving binders' stress relaxation capability,which results in less stress accumulation. At 5% and 10% modificationwith bio-adhesive, the specimens were too soft to be tested and theirdeflections were above the equipment range. Without being bound bytheory, it is expected that the improvement in low temperatureproperties of the binder results in reduced low temperature cracking dueto the general reduction in binder stiffness and increase in m-value. Inthis way, the addition of a robust soft bio-binder exemplifies theproperties of a bio-extender. When the refining process for asphaltremoves too much ‘soft’ material, the bio-binder acts as an effectivebio-extender, softening the bio-modified asphalt.

Example C1. Preparation of Bio-Modified Asphalt Binder

The bio-adhesive sample from Example 2d having a viscosity of 0.5 cP at135° C. was combined with PG52-28 asphalt binder at a loading of 5%bioadhesive by weight asphalt binder to create BMB-PG52-28-5. The basebinder and bio-binder were mixed thoroughly at shear rate of 3000 rpmfor 30 minutes at 124° C. The resulting bio-modified binder wascompacted at 113° C. according to standard methods, e.g. AASHTO T 312(Gyratory compaction of HMA Mixtures).

To evaluate the effect of the addition of the 5% bio-binder to thevirgin binder, the bio-modified and virgin binders were tested todetermine their rheological properties and performance grade inaccordance with AASHTO R29.

Viscosity testing results indicated that the bio-modified binder had areduced viscosity, as compared to the virgin binder. Lower binderviscosity can lead to a more workable mixture and this agrees with themixture workability results which indicated increased workability formixtures with the bio-modified binder. Without being bound by theory itis believed that mixtures produced with the bio-modified binder releasethermal stresses faster than petroleum-based asphalt binder therebyimproving the thermal characteristics of mixtures designed with thebio-modified binder.

Example C2. Preparation of Bio-Asphalt Mixture Comprising BMB and RAP

The effect of bio-modified asphalt binder prepared in Example C1 wasevaluated in combination with 40% recycled asphalt pavement (‘RAP’) and60% aggregate comprising 9.5 mm crushed stone, natural sand, stone sandand stone dust and developed to meet the requirements for a 9.5 mmSuperpave mixture in accordance with AASHTO M323 “Superpave VolumetricMix Design” and AASHTO R35 “Superpave Volumetric Design for Hot MixAsphalt.”

The properties of the bio-modified-RAP asphalt were compared to (1) acontrol sample comprising PG52-28 asphalt binder mixed with 9.5 mmSuperpave Mixture; (2) a sample comprising control of (1)+40% RAPmixture; and (3) a sample comprising control of (1)+5% bio-modifiedasphalt binder prepared in Example C1.

It is well known that improvements observed in asphalt binder studiesare not consistently reflected in asphalt mixtures, because the addedmaterials and increased number of variables lead to variations inproperties of asphalt mixtures. As shown herein, the addition of thebio-modified asphalt binder improved low temperature crackingproperties. It also improved the moisture resistance compared to thecontrol asphalt mixture that did not contain the bio-binder.

The addition of bio-modified binder reduces the stiffening effectscaused by the introduction of high percentages of reclaimed asphaltpavement (RAP) in the mixture. FIG. 5A shows a master curve,characterizing the stiffness of the mixtures over a wide range offrequencies and temperatures, and demonstrates that the incorporation of40% RAP to the control mixture increased its stiffness. Typically,negative effects are observed when the stiffness of the mixture gets toohigh—the mixture can become too brittle, which may result in thermalcracking. The introduction of the bio-modified binder decreased themixture stiffness for both the control and 40% RAP mixtures as comparedto the mixtures fabricated with PG52-28 binder. This indicated that thebio-modified binder reduced the stiffening effects caused by theintroduction of high percentages of RAP in the mixture. The data for thecontrol mixture fabricated with the bio-modified binder correspondedwell with the volumetric data, which showed a reduction in air voids atthe design gyration level, indicating the mixture is less stiff andeasier to compact.

As shown in FIG. 5C, the incorporation of 40% RAP reduced theworkability of the control mixture. This is consistent with the data inFIG. 5A because the 40% RAP mixture had higher stiffness as wasillustrated in the dynamic modulus master curves of the mixtures. Theaddition of the bio-modified binder improved the workability of the 40%RAP mixture. At temperatures below 280° F. (138° C.) the workability ofthe control mixture and the 40% RAP with bio-modified binders wereidentical, as illustrated in FIG. 5C. The control mixture with thebio-modified binder exhibited the lowest torque, consequently, bestworkability. As demonstrated herein, the viscosity of the bio-modifiedbinder was significantly lower than that of the base non-modifiedbinder; without being bound by theory the reduction in viscosity may bea contributing factor to the improved workability.

Example D. Preparation of an Asphalt Bio-Rejuvenator

The data in Example C further demonstrate that the bio-adhesive samplefrom Example 2d has properties of an asphalt bio-rejuvenator.

FIG. 5A, the master curve of dynamic modulus, shows that thebio-modified binder rejuvenated the 40% RAP mixture to the extent thatits properties were very close to the mixture with no RAP. In otherwords, bio-modified binder cancelled out the negative effect of oxidizedRAP on the dynamic modulus of the mixture. As shown in FIG. 5B, thepredicted and measured dynamic modulus, |E*|, the addition of thebio-modified binder to the composition comprising 40% RAP shifts thedynamic modulus of the composition back to that of the controlcomposition, comprising 0% RAP.

Without being bound by theory it is believed that the bio-adhesivesample replaces the ‘soft, light’ compounds that are lost as asphaltages, or oxidizes.

Example E. Preparation of Rubber Containing Bio-Asphalt

The bio-adhesive sample from Example 2d having a viscosity of 0.5 cP at135° C. was used in the preparation of rubber-containing bio-asphalt asdisclosed herein.

Crumb Rubber Gradation

The crumb rubber used for this experiment was obtained from reRubber LLCof Ontario, Canada. It was processed by ambient means, giving the samplemore size and shape consistency. The mesh size of the crumb rubber wasselected to be 80-200 as typically smaller particle size requires lessreaction time.

Bio Modified Rubber (BMR)

The binder was blended by means of the wet process using crumb rubberparticle sizes passing the No. 50 sieve. Wet process blending was usedto mix 80-200 mesh crumb rubber and petroleum based binder (PG 64-22) atthree percentages of crumb rubber (5%, 10%, and 15%) with one equivalentof the bio-adhesive of Example 2d (5%) by the weight of the petroleumbased binder. The blending was accomplished by means of a laterallyattached oscillating drill. Shearing was conducted at the speed of 1000rpm for 30 minutes at 200° C.

To study the temperature susceptibility of each binder, the VTS valueswere calculated based on Equation 1:

$\begin{matrix}{{VTS} = \frac{\left\lbrack {{\log\left( {\eta\; T_{2}} \right)} - {\log\left\lbrack {\log\left( {\log\left( {\eta\; T_{1}} \right)} \right\rbrack} \right.}} \right.}{{\log\left( T_{2} \right)} - {\log\left( T_{1} \right)}}} & (1)\end{matrix}$

T1 and T2 are the temperatures of the binder at known points, ηT1 andηT2 are the respected viscosities (cP) of the binder at those knownpoints. Typically, the magnitude of the VTS is directly proportional tothe temperature susceptibility of the binder. The results have beenplotted for CRM, BMR, and the control binder in FIG. 6A. As is shown,both BMR and CRM samples have lower slopes than that of the controlbinder indicating that the temperature susceptibility of binder wasreduced due the modification with rubber and bio-binder.

To investigate effects of rubber modification on shear susceptibility,the ‘shear susceptibility’ (‘SS’), defined as the rate of change ofviscosity with the rate of shear, was determined at differenttemperatures and plotted for both CMR and BMR in comparison with thecontrol binder (FIG. 6B). It can be seen that SS values for both BMR andCRM are higher than those of control asphalt; this is expected due tothe presence of rubber particles. Typically, when rubber is blended withasphalt, the rubber particles are swollen by absorption of the asphalt'soily phase into the polymer chains of crumb rubber to form a gel-likematerial. Unlike polymers, which disperse completely in the asphalt andcause changes in the molecular structure of the asphalt, crumb rubberkeeps its physical shape and behaves as flexible particulate filler inthe binder producing a non-homogeneous nature. This in turn, gives riseto shear susceptibility due to the movement of rubber particles relativeto each other in the binder matrix.

As shown, CRM has higher shear susceptibility than control asphalt; theaddition of bio-binder to a composition comprising crumb rubber led to areduction in shear susceptibility. Without being bound by theory, thereduction in shear susceptibility can be attributed to high oily phaseof bio-binder which can be easily absorbed by rubber particles toenhance swelling. This in turn will produce a gel-like matrix, which ismore homogenous and less susceptible to shear compared to anon-homogeneous matrix of flexible rubber particles that can easilyshear against each other.

Example F. Preparation of Nanoclay-Containing Bio-Asphalt

Materials

The test materials used in this study are virgin asphalt binder PG 58-28from Gladstone, Mich., United States of America, nano-modified asphaltbinder containing 2% and 4% nano silica and 2% and 4% Closite 30B (allby weight of base asphalt) from Southern Clay Products, Inc. and thebio-adhesive analogous to Example 2d (5% by weight of base asphalt),prepared according to Example 2, except that the thermochemicalliquefaction process was run at 360° C. for 15 min at 10.5 MPa. Thebio-adhesive was isolated as described in Example 2.

Fabrication of Asphalt Nano Composite

The nano-modified asphalt materials were prepared using a high shearmixer. The bitumen was first heated at about 135° C. until it becamefluid in the mixer. Then 2% and 4% nanoclay (by weight of base binder)was added to the asphalt, and the mixture was blended at 5,000 rpm for 2h. The nano-silica asphalt composite was processed under the sameconditions.

Fabrication of Bio-Modified Binder Nanocomposites

The bio-adhesive described above was added to the base asphalt binder(PG58-28) at a rate of 5% by weight of asphalt binder to create thebio-modified binder. The blending of base binder and bio-adhesive wasaccomplished by means of a shear mixer. Shearing was conducted at thespeed of 1,600 rpm for 30 minutes at 120° C.

The bio-modified binder nanocomposite was prepared by adding 5% ofbio-binder by weight of asphalt binder to base binder (PG58-28), andblending at 3,000 rpm for 10 min while temperature was kept at 120° C.After 10 min, 2% and 4% by weight of nanoclay and nanosilica was addedto the mixture blending at 5,000 rpm for 20 min with the temperaturekept at 120° C.

Rolling Thin Film Oven Short Term Aging Procedure

A Pressure Aging Vessel, conforming to ASTM 6521-08, was used to performlong term-aging, Rolling Thin Film Oven aging, in accordance with ASTM D2872-04.

The addition of bio-binder enhanced the high temperature performance andimproved the aging resistance of nanoparticle containing asphalt. Asshown in FIG. 7A, the aging resistance of each of the 2% and 4%nanoparticle-containing asphalt decreased compared to the controlbinder, based on the calculated viscosity aging index (VAI), which iscalculated by measuring the viscosity of the sample before and aftershort term rolling thin film oven:

${VAI} = \frac{{{RTFO}\mspace{14mu}{aged}\mspace{14mu}{viscosity}\mspace{14mu}{value}} - {{Unaged}\mspace{14mu}{viscosity}\mspace{14mu}{value}}}{{Unaged}\mspace{14mu}{Viscosity}\mspace{14mu}{value}}$

While there was no significant difference between the effectiveness ofnanoclay and nanosilica on the aging of control asphalt, the addition ofbio-binder affected the nanoparticle-containing asphalts differently.Without being bound by theory, this property is attributed to higheraffinity of bio-binder for silicate layers in nanoclay giving rise to adegree of exfoliation.

Addition of bio-binder to these asphalts improved the aging resistanceand for the nanoclay-containing asphalts, the viscosity aging index ison par to the control asphalt.

As shown in FIG. 7B, the addition of 2% nanoclay increased viscosity ofthe control binder by 22% on average and the addition of 4% nanoclayincreased it by an average of 36% within the temperature range (120° C.to 190° C.). The addition of bio-binder to the control asphalt binderdecreased the viscosity by an average of 16%. The addition of bio-binderto the 2% and the 4% nanoclay samples increased viscosity by an averageof 13% and 57%, respectively.

Example 3. Isolation of Components From Bio-Oil Produced From AnimalWaste

In one variation, an apparatus 200 as disclosed in FIG. 2 can be usedfor post-processing bio-oil prepared from animal waste comprising beef,dairy, poultry, sheep, or swine manure or combinations thereof. In afirst processing step, product mixture 204 of bio-char+bio-oil+solventis added to filtration device 202, which captures the insolublebio-char. The bio-oil in solution is transferred in the direction ofarrow A to vacuum distillation apparatus 206, which is heated by thedesignated heater 222, at temperatures in accordance with the methodsdisclosed herein. Pressures are monitored with vacuum gauge 208. Solvent210 is first driven off, followed by the light liquid fraction 212. Theheavy liquid fraction 214 can be (1) separately collected as anamide-compound containing fraction and a fraction with a lowconcentration of amide-containing products or (2) left in the pot liquorand collected in combination with the remaining bio-residue. Eachvolatile fraction can be condensed in condenser 215 and isolated fromcollection tank 224 via condensate drain 234. The viscosity of theremaining residue is determined based on the level of torque required tostir the residue, as shown in FIG. 2. The residue product P flows athigher temperatures, for example at the terminal distillationtemperatures disclosed herein and the bio-residue product P can becollected by pumping the ‘liquid’ over an optional dessicator 216 toremove odorous volatile compounds.

Example 3a: Isolation of Black Water

The reaction mixture, including bio-oil, solid and aqueous phases, fromExample 1b was vacuum filtered, isolating the aqueous phase, referred toas black water, which contains insignificant quantities of pathogens andcan be used as a fertilizer.

Example 3b: Isolation of Bio-Char

The sticky residue from the vacuum filtration of Example 3a was rinsedwith 10-50% solvent (either acetone or a 30:70 acetone/toluene mixture)and filtered, separating the insoluble bio-char from the bio-oil insolution in the filtrate.

Example 3c: Isolation of Light Liquid Fraction From Bio-Oil

The filtrate from Example 3b was placed in a vacuum distillationapparatus and the pressure in the apparatus was lowered to 3 mm Hg.

The gaseous fractions of the bio-oil, the solvent (acetone oracetone/toluene mix) and the Light Liquid Fraction were collected viavacuum distillation at 3 mm Hg using a heating rate of 15° C. to 30° C.per hour up to a distillation temperature of 60° C.

Example 3d: Isolation of Heavy Liquid Component Containing HighConcentration of Amide Groups From Bio-Oil

The pot liquor from Example 3c was further vacuum distilled at 3 mm Hgusing a heating rate of 15° C. to 30° C. per hour from 60° C. to 100° C.for collection of the Heavy Liquid Fraction containing amide compounds.

When the collection of the first heavy liquid fraction was completed,the condensed sample had a viscosity of about 0.1 cP. The sample alsocontained 10-20% amide compounds, as determined by FT-IR.

This Heavy Liquid Fraction containing amide compounds can be useful as abio-adhesion promoter and optionally as a bio-extender orbio-rejuvenator.

Example 3e: Isolation of Heavy Liquid Component Containing LowConcentration of Amide Groups From Bio-Oil

The pot liquor from Example 2c was further vacuum distilled at 3 mm Hgusing a heating rate of 15° C. to 30° C. per hour from 100° C. to 160°C. for collection of the Heavy Liquid Fraction containing a lowconcentration of amide compounds.

When the collection of the second heavy liquid component was completed,the condensed sample had a viscosity of about 0.1 cP. The samplecontained amide-containing compounds, but at a lower concentrationcompared to the fraction of Example 3d.

This Heavy Liquid Fraction containing low amounts of amide compounds canbe useful as a bio-extender or bio-rejuvenator.

Example 3f: Isolation of Bio-Residue

As disclosed herein, the quality of the bio-residue from the vacuumdistillation of the volatile components of the bio-oil is dependent on anumber of factors, including accurate control of distillation parametersas well as monitoring the viscosity of the residue.

During isolation of the components in Examples 3c to 3e, the viscosityof the remaining residue was monitored every 10 minutes and was notallowed to rise above about 0.5 cP at 135° C. After isolation of theother components disclosed, the remaining bio-residue was isolated fromthe distillation apparatus by pouring the still flowable residue into acollection flask.

The isolated bio-residue can be used in a variety of applications asdisclosed herein.

Example G. Preparation of a Bio-Adhesion Promoter

The heavy liquid component with amide compounds isolated in Example 3dhaving a viscosity of about 0.1 cP, but optionally having a viscositybetween about 0.1 cP and about 0.3 cP at 135° C., can be combined withbitumen at between about 0.1% and about 5% by weight. Alternately, theheavy liquid component with amide-containing compounds can be combinedwith bitumen in amounts between about 0.5% and about 3% or between about1% and about 2%.

The bio-modified adhesion promoter improves adhesion properties comparedto virgin bitumen, as measured by a direct adhesion test of a mixture ofbio-modified adhesion promoter and aggregate, evaluating the change inadhesion due to exposure to room temperature water. Without being boundby theory, the improved properties of the bio-modified asphalt are basedin part on the inclusion of the Heavy Liquid Fraction having amidecompounds, which promote adhesion of the asphalt to the aggregate asdisclosed herein.

Example H. Preparation of a Bio-Adhesion Promoter

The heavy liquid fraction isolated in Example 3d having a viscosity ofabout 0.1 cP, but optionally having a viscosity between about 0.1 cP andabout 0.3 cP at 135° C., can be combined with bitumen in amounts betweenabout 0.1% and about 10% by weight to yield industrially usefulbio-adhesion promoter. Alternately, the heavy liquid component withamide-containing compounds can be combined with bitumen in amountsbetween about 1% and about 8% or between about 2% and about 5% orbetween about 0.5% and about 3% or between about 1% and 2%.

The bio-modified adhesion promoter improves adhesion properties comparedto virgin bitumen, as measured by a direct adhesion test of a mixture ofbio-modified adhesion promoter and aggregate, evaluating the change inadhesion due to exposure to room temperature water.

The bio-adhesion promoter of the present application can be also used asWarm Mix Additive to 1) allow for reduction of mixing and compactiontemperature; 2) to enhance workability; and 3) to increase moisturedamage resistance. Introduction of bio-adhesive promoter to bitumenusing an in-line blending in the asphalt plant can enhance workabilityof the resulting mixture by reducing the viscosity of the bitumen.Usually the bio-adhesive promoter is combined at about 1% to about 10%by weight with bitumen, for example the bio-adhesive component iscombined at about 1% or about 2% or about 3% or about 4% or about 5% orabout 6% or about 7% or about 8% or about 9% or about 10% by weight withbitumen.

Example I. Preparation of an Asphalt Bio-Extender

The heavy liquid fraction isolated in either Example 3d or Example 3e,each having a viscosity of about 0.1 cP, but optionally between about0.1 cP and about 0.5 cP at 135° C., can each be combined at betweenabout 1% and about 75% by weight with bitumen to yield industriallyuseful asphalt bio-extenders. Typically, the amount of bio-extender isbetween about 5% and about 50% by weight of petroleum-based asphalt.

Without being bound by theory, it is believed that the optimizedviscosity of the Heavy Liquid Fraction with or without amide-containingcompounds enables the fractions to be effective asphalt bio-extenders.Specifically, the Heavy Liquid Fraction is incorporated into a RAP/RAScontaining asphalt formulation, wherein the RAP+RAS fraction is betweenabout 30% and about 40%. The dynamic modulus measurement shows that thedynamic modulus of the Heavy Liquid Fraction-containing formulationcorresponds well to the control formulation comprising petroleum-basedasphalt with no RAP/RAS.

Example J. Preparation of an Asphalt Bio-Rejuvenator

The heavy liquid fraction isolated in either Example 3d or Example 3e,each having a viscosity of between about 0.1 cP and about 0.5 cP, caneach be combined at between about 1% and 50% by weight with bitumen toyield industrially useful asphalt bio-rejuvenators.

Consistent with the results in Example D, changes to the dynamic modulusupon addition of the heavy liquid fraction shows that the bio-adhesivecomponent is an effective bio-rejuvenator and replaces the ‘soft, light’compounds that are lost as asphalt ages or oxidizes.

Example K. Preparation of Bio-Modified Binder (BMB)

The bio-residue isolated in Example 3f having a viscosity of about 0.5cP, but optionally having a viscosity between about 0.4 cP and 1 cP, at135° C. is combined with an asphalt binder at between about 2% and about10%, typically about 5% by weight, using a low shear mixer at 100° C.for at least about 20 minutes, yielding a bio-modified binder havingimproved properties compared to a petroleum-based asphalt binder.

Example L. Preparation of Nanoclay-Containing Bio-Asphalt

The bio-residue isolated in Example 3f having a viscosity of about 0.5cP at 135° C., but optionally having a viscosity between about 0.4 cPand 1 cP, is combined with between about 4% and about 10% by weightorganonanoclay as identified in Example F using a high shear mixer for30 minutes at 100° F. yielding a brittle aging resistant nanoclaycontaining bio-asphalt.

Example M. Preparation of Rubber-Containing Bio-Asphalt

The bio-residue isolated in Example 3f having a viscosity of 0.5 cP at135° C., but optionally having a viscosity between about 0.4 cP and 1cP, is combined with rubber as identified in Example E, using a highshear mixer for 1 hour at 100° F., yielding a flexible stand alonerubber containing bio-asphalt.

Consistent with the results in Example E, the rubber-containingbioasphalt of the present example demonstrates improved temperaturesusceptibility and shear susceptibility compared to the product madewithout the bio-residue.

Example N. Use of Bio-Residue with PG Graded Asphalt

The bio-reside isolated in Example 3f having a viscosity of about 0.5cP, but optionally having a viscosity between about 0.4 cP and 1 cP at135° C., is combined with PG64-22 (at 2%, 5% or 10% bio-binder perasphalt binder by weight) to produce bio-modified binder. Bio-binder andbase binder are heated to 60° C. and 120° C., respectively. The basebinder and bio-binder are mixed thoroughly at shear rate of 3000 rpm for30 minutes, while the temperature is kept at 120° C.

Example O. Use of Bio-Residue as Bio-Asphalt

The bio-residue isolated in Example 3f having a viscosity of about 0.5cP, but optionally having a viscosity between about 0.4 cP and 3 cP orbetween about 0.5 cP and 1 cP at 135° C. can also be used as abio-asphalt without any modifications (such as rubber or nanoclay). Sucha bio-asphalt can be used either with or without addition ofpetroleum-based asphalt.

The bio-asphalt of the present example demonstrates industrially usefulproperties, as tested by BBR and DSR (dynamic shear rheometer).

Example P. Use of Bioasphalts as Sealant and Crack Filler

The bioasphalts of the present application can also be used in sealingand filling asphalt concrete pavement cracks. In particular, bioasphaltsincluding but not limited to pure bio-asphalt, modified bio-asphalt, andrubber-containing bioasphalt, are placed into or above cracks, generallyto prevent the intrusion of water and material impurities into thecracks and to reinforce the pavement adjacent to the cracks.

Example Q. Use of Bio-Asphalt in Roofing

Bio-adhesives of the present application are used in liquid asphaltroofing, (or ‘hot mop method’). In this example the bio-asphalt asprepared in Example 3f, Example K, Example M, Example N, or Example O isinstalled by spreading hot bio-asphalt over a roof. After application ofthis adhesive to a typically flatter roof, a layer of decorative rocksis distributed on top of the hot asphalt.

Example R. Use of Bioasphalts as Flooring Bio-Adhesive

Bioasphalts of the present application as prepared in Example 3f,Example K, Example N and Example O can also be used as a flooringbio-adhesive. In one aspect, bio-adhesives can replace petroleum-basedadhesives which are used to install a wood floor over a cement slab.Alternately, the flooring adhesive can be used as a carpet adhesive.Such products can be evaluated according to ASTM D6004-04(2011)“Standard Test Method for Determining Adhesive Shear Strength of CarpetAdhesives” and ASTM D6005-03(2009) “Standard Test Method for DeterminingSlump Resistance of Carpet Adhesives.”

The patents and publications listed herein describe the general skill inthe art and are hereby incorporated by reference in their entireties forall purposes and to the same extent as if each was specifically andindividually indicated to be incorporated by reference. In the case ofany conflict between a cited reference and this specification, thespecification shall control. In describing embodiments of the presentapplication, specific terminology is employed for the sake of clarity.However, the invention is not intended to be limited to the specificterminology so selected. Nothing in this specification should beconsidered as limiting the scope of the present invention. All examplespresented are representative and non-limiting. The above-describedembodiments may be modified or varied, without departing from theinvention, as appreciated by those skilled in the art in light of theabove teachings. It is therefore to be understood that, within the scopeof the claims and their equivalents, the invention may be practicedotherwise than as specifically described.

What is claimed:
 1. A bio-adhesive composition comprising a heavy liquidfraction and a bio-residue, wherein the composition has a viscosity ofabout 0.5 cP at 135° C., wherein said heavy liquid fraction andbio-residue are isolated from bio-oil produced from animal waste andwherein said bio-adhesive composition does not contain a light liquidfraction from said bio-oil.
 2. The bio-adhesive composition of claim 1,wherein the composition is free of compounds that have a boiling pointat 3 mm Hg of less than 60° C.
 3. The bio-adhesive composition of claim1, wherein the animal waste comprises beef manure, dairy manure, swinemanure, sheep manure, poultry manure or combinations thereof.
 4. Thebio-adhesive composition of claim 3, wherein the animal waste comprisesswine manure comprising at least about 30% solid manure.
 5. Abio-adhesive composition comprising a heavy liquid fraction having aviscosity of between about 0.1 cP and about 0.5 cP at 135° C., whereinsaid heavy liquid fraction is isolated from bio-oil produced from animalwaste and said bio-adhesive composition does not contain a light liquidfraction from said bio-oil.
 6. The bio-adhesive composition of claim 5,wherein the composition is free of compounds that have a boiling pointat 3 mm Hg of less than 60° C.
 7. The bio-adhesive composition of claim5, wherein the bio-adhesive composition comprises: (a) a heavy liquidfraction comprising at least about 5% by weight of amide-containingcompounds, or (b) a heavy liquid fraction comprising up to about 5% byweight of amide-containing compounds.
 8. The bio-adhesive composition ofclaim 7, wherein the bio-adhesive composition comprises a heavy liquidfraction comprising at least about 5% by weight of amide-containingcompounds.
 9. The bio-adhesive composition of claim 8, wherein thebio-adhesive composition comprises a heavy liquid fraction comprising atleast about 10% by weight of amide-containing compounds.
 10. Thebio-adhesive composition of claim 9, wherein the bio-adhesivecomposition comprises a heavy liquid fraction comprising at least 15% byweight of amide-containing compounds.
 11. The bio-adhesive compositionof claim 9, wherein the bio-adhesive composition comprises a heavyliquid fraction comprising 10-20% by weight of amide-containingcompounds.
 12. The bio-adhesive composition of claim 11, wherein thecomposition has a viscosity of about 0.1 cP.
 13. The bio-adhesivecomposition of claim 7, wherein the composition has a viscosity of about0.1 cP.
 14. The bio-adhesive composition of claim 5, wherein the animalwaste comprises beef manure, dairy manure, swine manure, sheep manure,poultry manure or combinations thereof.
 15. The bio-adhesive compositionof claim 14, wherein the animal waste comprises swine manure.
 16. Thebio-adhesive composition of claim 15, wherein the swine manure comprisesat least about 30% solid manure.
 17. A bio-adhesive compositioncomprising a bio-residue having a viscosity of at least about 0.4 cP at135° C., wherein said bio-residue is isolated from bio-oil produced fromanimal waste, and wherein said bio-adhesive composition does not containa light liquid fraction from said bio-oil.
 18. The bio-adhesivecomposition of claim 17, wherein the composition is free of compoundsthat have a boiling point at 3 mm Hg of less than 60° C.
 19. Thebio-adhesive composition of claim 17, wherein the animal waste comprisesbeef manure, dairy manure, swine manure, sheep manure, poultry manure orcombinations thereof.
 20. The bio-adhesive composition of claim 19,wherein the animal waste comprises swine manure comprising at leastabout 30% solid manure.